CN113929113A - 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 127
- 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 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 53
- 238000002425 crystallisation Methods 0.000 claims abstract description 49
- 230000008025 crystallization Effects 0.000 claims abstract description 49
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011148 porous material Substances 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 26
- 239000011574 phosphorus Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 86
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 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
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 21
- 239000002245 particle Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 9
- 239000002149 hierarchical pore Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 241000269350 Anura Species 0.000 description 3
- 238000000926 separation 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 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
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 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
- 239000004148 curcumin Substances 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 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
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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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- B01J35/617—
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- B01J35/633—
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- B01J35/635—
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- B01J35/69—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/04—Ethylene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
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- C07C11/06—Propene
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2006/12—Surface area
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention discloses an SAPO-34 molecular sieve, a preparation method and an application 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 has a cubic-like shape, a mesoporous/macroporous structure penetrates through the whole crystal along a direction vertical to a cubic-like surface, and the pore size distribution of the mesoporous/macroporous structure is 10-1500 nm, so that a good catalytic effect can be obtained when the mesoporous/macroporous structure is used for a reaction for preparing olefin from methanol.
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 prepared from AlO4、SiO4And PO4The tetrahedra form a three-dimensional crystal structure by sharing oxygen atoms, in which Si is present in the channels of the crystal4+Partially substituted P5+Or Al3+Producing acidity. SAPO series molecular sieves have good thermal stability and hydrothermal stability, moderate acidity, higher specific surface area and highly ordered microporous pore canals, 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 Olefin (MTO) reactions: the conversion rate of the methanol reaches 100 percent; the selectivity of ethylene and propylene can exceed 70 percent; c5+The content of the components is small and almost no aromatic hydrocarbon is generated. However, the pore size of the SAPO-34 molecular sieve is 0.38nm, and is an eight-membered ring pore, which presents a serious shape-selective limitation, on one hand, the contact of raw material molecules with active centers inside the pore is blocked, on the other hand, the diffusion and mass transfer of reactants, intermediate transition products and final products are limited, and the pore is easily 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 subject to more stringent conditions for post-treatment because phosphoaluminosilicate molecular sieves have less stability than aluminosilicate molecular sieves, require precise control of conditions for 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-. Kaskel et al added carbon materials (carbon nanotubes and carbon nanoparticles) during the synthesis of SAPO-34 molecular sieves, and eventually formed mesopores in the large SAPO-34 molecular sieve particles, either embedded within the molecular sieve crystals or throughout the entire crystal particle (F. Schmidt, S. Paasch, E.Brunner and S.Kaskel, Microporous Mesoporous Mater.,2012,164, 214-221.). 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 and chrysolel, etc. are hydrothermally synthesized into SAPO-34 molecular sieve with hierarchical pore structure with multifunctional long-chain organosilicon as silicon source, respectively (chrysolel, Wangru Wei, Ding, etc. chemical reports of higher schools 2010; 31(9): 1693-; liuzhong et al (J.Mater.chem.A. 2015,3, 5608-; cui et al (Cui Y, Zhang Q, He J, et al. Particuology, 2013; 11(4): 468-.
In summary, although the preparation of the existing hierarchical pore materials is a hot point of research by researchers, the hierarchical pore SAPO-34 meso/macroporous pore volume synthesized by the existing method for preparing the hierarchical pore SAPO-34 molecular sieve is low or the cost of the used pore-forming agent is high. Therefore, the preparation route of the synthetic multi-stage pore SAPO-34 molecular sieve, which is simple in development method and low in cost, has important practical significance.
Disclosure of Invention
Aiming at the problems that the SAPO-34 molecular sieve with a multilevel pore channel structure synthesized by the prior art is low in meso/macroporous pore volume or high in preparation cost, the invention provides the SAPO-34 molecular sieve which has a cubic-like shape, and a large number of meso/macropores exist in the molecular sieve crystal, are orderly arranged and have high meso/macroporous pore volume.
The invention provides an SAPO-34 molecular sieve which is in a cubic-like shape, a mesoporous/macroporous structure penetrates through the whole crystal along a direction vertical to a cubic-like surface, and the pore size distribution of mesopores/macropores is 10-1500 nm.
Further, the longest side length of the cubic-like body of the SAPO-34 molecular sieve is 10-30 mu m.
Furthermore, the pore size distribution of mesopores of the SAPO-34 molecular sieve is 10-25 nm, and the pore size distribution of macropores is 100-1500 nm.
Further, the specific surface area of the molecular sieve is 550-600 m2Per gram, preferably 570-593 m2Per gram; the micropore volume of the molecular sieve is 0.27-0.28 cm3Per gram, preferably 0.276-0.279 cm3G, total pore volume of the mesopores and the macropores is 0.3-1.1 cm3Per gram, preferably 0.7 to 0.9 cm3Per gram.
Furthermore, the macropore volume accounts for 90-97% of the total mesopore volume of the mesopores/macropores.
The invention provides a preparation method of the 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;
wherein the structure directing agent is triethylamine; wherein the molecular formula of the auxiliary structure directing agent is as follows:
wherein the step of crystallization treatment adopts dynamic crystallization.
Further, the aluminum source is pseudo-boehmite; 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 auxiliary structure directing agent, the aluminum source is Al2O3In terms of phosphorus source H3PO4The silicon source is SiO2Based on the raw material ratio, namely Al2O3：H3PO4: structure-assisting directing agent: structure directing agent: SiO 22：H2The molar ratio of O is (0.7-1.3): (1.4-3.0): (0.3-1.8): (2-5): (0.2-0.9): (40-90).
Further, the crystallization adopts dynamic crystallization, and the crystallization conditions are as follows:
the first stage is as follows: the crystallization temperature is 170-190 ℃, and the crystallization time is 20-80 hours; and a second stage: the crystallization temperature is 195-210 ℃, the crystallization time is 5-30 hours, and the third stage is as follows: the crystallization temperature is 100-150 ℃, 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 the mixture for 2 to 12 hours at the temperature of between 20 and 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-1.0 MPa, the reaction temperature is 390-515 ℃, and the methanol feeding weight space velocity is 1-E100 hours-1。
Compared with the prior art, the invention has the following advantages:
1. the SAPO-34 molecular sieve provided by the invention is of a cubic-like shape, a meso/macroporous structure penetrates through the whole crystal along a direction vertical to the cubic-like surface, wherein the macroporous volume accounts for 90-97% of the total mesoporous/macroporous volume, and the meso/macroporous volume of the SAPO-34 molecular sieve is higher.
2. In the preparation method of the SAPO-34 molecular sieve, the pure-phase and ordered mesoporous SAPO-34 molecular sieve is synthesized by adopting the specific auxiliary structure guiding agent and utilizing the matching action among the raw materials, particularly designing the specific dynamic crystallization process.
3. The SAPO-34 molecular sieve has the advantages of simple preparation method, low equipment requirement and high product yield, so the SAPO-34 molecular sieve has good industrial application prospect.
Drawings
FIG. 1 is an XRD pattern of SAPO-34 molecular sieves obtained in examples 1-4 of the invention;
FIG. 2 is an XRD pattern of the molecular sieves obtained in comparative examples 1-4;
FIG. 3 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. 4 is an SEM image of a SAPO-34 molecular sieve obtained in example 2 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. 5 is an SEM image of a SAPO-34 molecular sieve obtained in 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. 6 is an SEM image of a SAPO-34 molecular sieve obtained in example 4 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. 7 is an SEM image of the SAPO-34 molecular sieve obtained in comparative example 1; wherein the left part is the overall appearance of the molecular sieve, and the right part is a local enlarged view;
FIG. 8 is an SEM image of the molecular sieve obtained in comparative example 2; wherein the left part is the overall appearance of the molecular sieve, and the right part is a local enlarged view;
FIG. 9 is an SEM image of the molecular sieve obtained in comparative example 3; wherein the left part is the overall appearance of the molecular sieve, and the right part is a local enlarged view;
FIG. 10 is an SEM image of the molecular sieve obtained in comparative example 4; wherein the left part is the overall appearance of the molecular sieve, and the right part is a local enlarged view.
Detailed Description
In the context of the present description, including in the following examples and comparative examples, the XRD data were measured with an X-ray diffractometer model brueck AXS D8Advance, germany, under 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 context of the present description, including in the following examples and comparative examples, SEM pictures were taken from the HITACHI S4800 field emission scanning electron microscope under test conditions of 3KV and a current of 10 μ a. The present invention is further illustrated by the following examples, which are not intended to limit the scope of the present invention.
In the context of the present specification, including the following examples and comparative examples, the pore volume and the specific surface area of the molecular sieve are measured by the nitrogen physical adsorption and desorption method (BET method): the nitrogen physical adsorption and desorption isotherm of the molecular sieve was measured by a physical adsorption apparatus (Micromeritics TriStar3000 physical adsorption apparatus) and calculated by the BET equation and the t-plot equation. The experimental conditions were: the temperature was measured at 75K and the molecular sieves were pre-treated in vacuo at 350 ℃ for 4 hours before measurement.
In the context of the present specification, including the examples and comparative examples below, the mesoporous, macroporous volumes, and the ratio of macroporous volumes to the total mesoporous/macroporous volumes of the molecular sieve were determined by mercury intrusion, using Thermo Electron Pascal 140/240.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the present invention.
The molecular formula of the structure-assisting directing agent used in the examples and comparative examples of the present invention is:
[ example 1 ]
With silica sol (40% by weight SiO)2) Pseudo-boehmite (70 wt% Al)2O3) And phosphoric acid (85 wt% H)3PO4) 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, the triethylamine TEA and the structure directing agent are added into water to be mixed, and the raw materials are Al in the molar ratio2O3：H3PO4: structure-assisting directing agent: structure directing agent: SiO 22：H2The molar ratio of O is 1.0: 2.0: 0.7: 3.0: 0.38: 72. the mixture is rotated and crystallized for 60 hours at 180 ℃ and the rotating speed of 20 r/min, then the temperature is raised to 200 ℃, the rotation and crystallization are continued for 20 hours, then the temperature is lowered 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 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 of 2 theta at 9.5o, 15.9o, 20.5o, 26o and 31o belong to the SAPO-34 molecular sieve.
As shown in FIG. 3, the molecular sieve has a cubic morphology, and it can be seen from some broken particles that the multilevel pores are distributed in the whole crystal, and are arranged orderly, and the outer surface of the molecular sieve is convex. The molecular sieve has the mesoporous distribution of 10-25 nm, the macroporous distribution of 100-1500 nm, and the macroporous volume accounts for 97% of the total mesoporous/macroporous volume. The longest side of the cubic-like form of the SAPO-34 molecular sieve is 22 μm. Other properties are shown in table 2.
As shown in Table 1, the WHSV was 6h-1And under the reaction condition of 460 ℃, methanol is used as a raw material, the molecular sieve in the embodiment 1 is adopted for the reaction of preparing olefin from methanol, the diene yield can reach 84.85 percent, and a good catalytic effect is shown.
[ example 2 ]
With silica sol (40% by weight SiO)2) Pseudo-boehmite (70 wt% Al)2O3) And phosphoric acid (85 wt% H)3PO4) 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, the triethylamine TEA and the structure directing agent are added into water to be mixed, and the raw materials are Al in the molar ratio2O3：H3PO4: structure-assisting directing agent: structure directing agent: SiO 22：H2The molar ratio of O is 1.0: 2.0: 1.05: 3.0: 0.38: 72. the mixture is rotated and crystallized for 60 hours at 180 ℃ and the rotating speed of 20 r/min, then the temperature is raised to 200 ℃, the rotation and crystallization are continued for 20 hours, then the temperature is lowered 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 pattern of the sample is shown in figure 1, and diffraction peaks at 9.5o, 15.9o, 20.5o, 26o and 31o of 2 theta belong to SAPO-34 molecular sieves.
As shown in FIG. 4, the molecular sieve has a cubic morphology, and it can be seen from some broken particles that the multilevel pores are distributed in the whole crystal, and are arranged orderly, and the outer surface of the molecular sieve is convex. The molecular sieve has the mesoporous distribution of 10-25 nm, the macroporous distribution of 100-1500 nm, and the macroporous volume accounts for 94% of the total mesoporous/macroporous volume. The longest side of the cubic-like form of the SAPO-34 molecular sieve is 20 μm. Other properties are shown in table 2.
[ example 3 ]
With silica sol (40% by weight SiO)2) Pseudo-boehmite (70 wt% Al)2O3) And phosphoric acid (85 wt% H)3PO4) 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, the triethylamine TEA and the structure directing agent are added into water to be mixed, and the raw materials are Al in the molar ratio2O3：H3PO4: structure-assisting directing agent: structure directing agent: SiO 22：H2The molar ratio of O is 1.0: 2.0: 1.76: 3.0: 0.38: 72. the mixture is inRotating at 180 deg.C at 20 rpm for 60 hr, heating to 200 deg.C, rotating for 20 hr, cooling to 120 deg.C, and rotating for 10 hr. 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 pattern of the sample is shown in figure 1, and diffraction peaks at 9.5o, 15.9o, 20.5o, 26o and 31o of 2 theta belong to SAPO-34 molecular sieves.
As shown in FIG. 5, the molecular sieve has a cubic morphology, and it can be seen from some broken particles that the multilevel pores are distributed in the whole crystal, and are arranged orderly, and the outer surface of the molecular sieve is convex. The molecular sieve has the mesoporous distribution of 10-25 nm, the macroporous distribution of 100-1500 nm, and the macroporous volume accounts for 95% of the total mesoporous/macroporous volume. The longest side of the cubic-like form of the SAPO-34 molecular sieve is 23 μm. Other properties are shown in table 2.
[ example 4 ]
With silica sol (40% by weight SiO)2) Pseudo-boehmite (70 wt% Al)2O3) And phosphoric acid (85 wt% H)3PO4) 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, the triethylamine TEA and the structure directing agent are added into water to be mixed, and the raw materials are Al in the molar ratio2O3：H3PO4: structure-assisting directing agent: structure directing agent: SiO 22：H2The molar ratio of O is 1.0: 2.0: 1.05: 3.0: 0.38: 35. the mixture is rotated and crystallized for 60 hours at 180 ℃ and the rotating speed of 20 r/min, then the temperature is raised to 200 ℃, the rotation and crystallization are continued for 10 hours, then the temperature is lowered 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 figure 1, and diffraction peaks appear at 9.5o, 15.9o, 20.5o, 26o and 31o in 2 theta, which indicates that the synthesized product is a pure SAPO-34 molecular sieve.
As shown in FIG. 6, the molecular sieve has a cubic morphology, and it can be seen from some broken particles that the multilevel pores are distributed in the whole crystal, and are arranged orderly, and the outer surface of the molecular sieve is convex. The molecular sieve has the mesoporous distribution of 10-25 nm, the macroporous distribution of 100-1500 nm, and the macroporous volume accounts for 92% of the total mesoporous/macroporous volume. The longest side of the cubic-like form of the SAPO-34 molecular sieve is 20 μm. Other properties are shown in table 2.
Comparative example 1
With silica sol (40% by weight SiO)2) Pseudo-boehmite (70 wt% Al)2O3) And phosphoric acid (85 wt% H)3PO4) 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 raw materials are Al in the molar ratio2O3：H3PO4: structure directing agent: SiO 22：H2The molar ratio of O is 1.0: 2.0: 3.0: 0.38: 72. the mixture is rotated and crystallized for 60 hours at 180 ℃ and the rotating speed of 20 r/min, then the temperature is raised to 200 ℃, the rotation and crystallization are continued for 20 hours, then the temperature is lowered 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. 2, and it can be seen from FIG. 2 that the synthesized molecular sieve has the characteristic diffraction peaks of SAPO-34 molecular sieve, and the diffraction peaks with 2 theta at 9.5o, 15.9o, 20.5o, 26o and 31o are attributed to SAPO-34.
As shown in FIG. 7, the molecular sieve appearance is tetragonal-like (typical of SAPO-34 molecular sieves), and the SAPO-34 particle size is 4-8 μm. No hierarchical pores exist on the SAPO-34 type cube particles.
The molecular sieve of comparative example 1 was used in a methanol to olefin reaction under the same evaluation conditions as in example 1; comparative example 1 the diene yield was 81.08% under the same reaction conditions, and the reaction life of comparative example 1 was shorter than that of example 1; therefore, the catalytic effect of the example 1 is obviously better than that of the comparative example 1, and the SAPO-34 synthesized by the method 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
With silica sol (40% by weight SiO)2) Pseudo-boehmite (70 wt% Al)2O3) And phosphoric acid (85 wt% H)3PO4) 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, the triethylamine TEA and the structure directing agent are added into water to be mixed, and the raw materials are Al in the molar ratio2O3：H3PO4: structure-assisting directing agent: structure directing agent: SiO 22：H2The molar ratio of O is 1.0: 2.0: 1.9: 3.0: 0.38: 72. the mixture is rotated and crystallized for 60 hours at 180 ℃ and the rotating speed of 20 r/min, then the temperature is raised to 200 ℃, the rotation and crystallization are continued for 20 hours, then the temperature is lowered 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 molecular sieve sample.
The XRD spectrum of the sample is shown in FIG. 2, and it can be seen from FIG. 2 that the synthesized molecular sieve has the characteristic diffraction peaks of the SAPO-34 molecular sieve, and the diffraction peaks appearing at 9.5o, 15.9o, 20.5o, 26o and 31o of 2 theta belong to the SAPO-34 molecular sieve; additionally, the diffraction peaks for 2 θ at 7.4o, 14.9o, 19.7o and 22.4o are assigned to SAPO-5.
As shown in FIG. 8, the molecular sieve has a cubic morphology, and it can be seen from some broken particles that the multilevel pores are distributed in the whole crystal. Meanwhile, hexagonal column particles exist in the sample, and are SAPO-5 molecular sieves.
Comparative example 3
With silica sol (40% by weight SiO)2) Pseudo-boehmite (70 wt% Al)2O3) And phosphoric acid (85 wt% H)3PO4) 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, the triethylamine TEA and the structure directing agent are added into water to be mixed, and the raw materials are Al in the molar ratio2O3：H3PO4: structure-assisting directing agent: structure directing agent: SiO 22：H2Mole of OThe ratio is 1.0: 2.0: 1.05: 3.0: 0.38: 72. the mixture is kept standing and crystallized for 60 hours at 180 ℃, then the temperature is raised to 200 ℃, the standing and crystallization are continued for 20 hours, then the temperature is lowered to 120 ℃, and the standing 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 molecular sieve sample.
The XRD spectrum of the sample is shown in FIG. 2, and it can be seen from FIG. 2 that the synthesized molecular sieve has the characteristic diffraction peaks of the SAPO-34 molecular sieve, and the diffraction peaks appearing at 9.5o, 15.9o, 20.5o, 26o and 31o of 2 theta belong to the SAPO-34 molecular sieve; while the diffraction peaks at 7.4, 14.9, 19.7 and 22.4 for 2 theta are ascribed to SAPO-5.
As shown in FIG. 9, the molecular sieve has a cubic morphology, and it can be seen from some broken particles that the multilevel pores are distributed on the whole particle. Meanwhile, hexagonal column particles exist in the sample, and are SAPO-5 molecular sieves.
Comparative example 4
With silica sol (40% by weight SiO)2) Pseudo-boehmite (70 wt% Al)2O3) And phosphoric acid (85 wt% H)3PO4) 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, the triethylamine TEA and the structure directing agent are added into water to be mixed, and the raw materials are Al in the molar ratio2O3：H3PO4: structure-assisting directing agent: structure directing agent: SiO 22：H2The molar ratio of O is 1.0: 2.0: 1.05: 3.0: 0.38: 72. the mixture is rotated and crystallized for 20 hours at the rotating speed of 20 r/min at the temperature of 200 ℃, 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 molecular sieve sample.
The XRD spectrum of the sample is shown in FIG. 2, and it can be seen from FIG. 2 that the synthesized molecular sieve has the characteristic diffraction peaks of the SAPO-34 molecular sieve, and the diffraction peaks appearing at 9.5o, 15.9o, 20.5o, 26o and 31o of 2 theta belong to the SAPO-34 molecular sieve; while the diffraction peaks at 7.4, 14.9, 19.7 and 22.4 for 2 theta are ascribed to SAPO-5.
As shown in FIG. 10, the molecular sieve has a cubic morphology, and it can be seen from some broken particles that the multilevel pores are distributed on the whole particle. Meanwhile, hexagonal column particles exist in the sample, and are SAPO-5 molecular sieves.
TABLE 1 catalysis results in methanol to olefins with the molecular sieve samples obtained in example 1 and comparative example 1
| Time, min | Ethylene, wt.% | Propylene, wt.% | Total amount of diene in wt% | |
| Example 1 | 70 | 51.32 | 33.53 | 84.85 |
| Comparative example 1 | 55 | 45.53 | 35.55 | 81.08 |
Note: in the present invention, the yield of each product is by mass.
TABLE 2 Properties of the molecular sieve samples obtained in the examples and comparative examples
Claims (10)
1. The SAPO-34 molecular sieve is in a cubic-like shape, a mesoporous/macroporous structure penetrates through the whole crystal along a direction vertical to a cubic-like surface, and the pore size distribution of mesopores/macropores is 10-1500 nm.
2. The molecular sieve of claim 1, wherein the SAPO-34 molecular sieve has a cuboidal shape with a longest dimension of 10 to 30 μ ι η.
3. The molecular sieve of claim 1, wherein the pore size distribution of the mesopores of the SAPO-34 molecular sieve is 10-25 nm, and the pore size distribution of the macropores is 100-1500 nm.
4. The molecular sieve of claim 1, wherein the molecular sieve has a specific surface area of 550 to 600 meters2Per gram, preferably 570-593 m2Per gram; the micropore volume of the molecular sieve is 0.27-0.28 cm3Per gram, preferably 0.276-0.279 cm3G, total pore volume of the mesopores and the macropores is 0.3-1.1 cm3Per gram, preferably 0.7 to 0.9 cm3Per gram; preferably, the macropore volume accounts for 90-97% of the total mesopore/macropore volume.
5. A preparation method of the SAPO-34 molecular sieve 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;
wherein the structure directing agent is triethylamine; the molecular formula of the auxiliary structure directing agent is as follows:
wherein the step of crystallization treatment adopts dynamic crystallization.
6. The method of claim 5 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.
7. The method of claim 5, 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 agent2O3In terms of phosphorus source H3PO4The silicon source is SiO2Calculated as Al2O3：H3PO4: structure-assisting directing agent: structure directing agent: SiO 22：H2The molar ratio of O is (0.7-1.3): (1.4-3.0): (0.3-1.8): (2-5): (0.2-0.9): (40-90).
8. The method of claim 5, wherein the crystallization is dynamic crystallization, and the crystallization conditions are as follows: the first stage is as follows: the crystallization temperature is 170-190 ℃, and the crystallization time is 20-80 hours; and a second stage: the crystallization temperature is 195-210 ℃, the crystallization time is 5-30 hours, and the third stage is as follows: the crystallization temperature is 100-150 ℃, and the crystallization time is 5-20 hours.
9. The method according to claim 8, wherein the dynamic crystallization is performed under stirring conditions, wherein the rotation speed is 5 to 50 rpm.
10. Use of the SAPO-34 molecular sieve of any one of claims 1 to 4 in a methanol to olefin reaction.
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