CN111410207A - Normal-pressure synthesis method of SAPO-11 molecular sieve - Google Patents
Normal-pressure synthesis method of SAPO-11 molecular sieve Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 75
- 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 75
- 238000001308 synthesis method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 27
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000002425 crystallisation Methods 0.000 claims description 41
- 230000008025 crystallization Effects 0.000 claims description 41
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 12
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 11
- 229940043279 diisopropylamine Drugs 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 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
- 238000005406 washing Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 21
- 230000015572 biosynthetic process Effects 0.000 abstract description 14
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- 230000002776 aggregation Effects 0.000 abstract description 5
- 238000004220 aggregation Methods 0.000 abstract description 5
- 230000006698 induction Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- -1 hydroxyl radicals Chemical class 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Classifications
-
- 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
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The invention belongs to the technical field of SAPO-11 molecular sieves, and discloses a normal-pressure synthesis method of an SAPO-11 molecular sieve. Adding water, an aluminum source, a phosphorus source, organic amine, a silicon source and a carbon material into a container in sequence according to a specific molar ratio, stirring to prepare sol, and heating and crystallizing the sol under a microwave condition to obtain a molecular sieve SAPO-11; the water and the aluminum source (Al)2O3Calculated as P), a source of phosphorus (calculated as P)2O5Calculated as SiO), organic amine, silicon source2Calculated by the formula, the molar ratio of the carbon material to the carbon material is (60-120):1.0:1.0: (1.1-1.4): 0.2-1.0: (0.01-0.50). The method has mild conditions, can smoothly synthesize the molecular sieve SAPO-11, can obviously shorten the synthesis induction period of the molecular sieve, and effectively inhibit the aggregation phenomenon of small crystal grains.
Description
Technical Field
The invention relates to an SAPO-11 molecular sieve, in particular to a normal pressure synthesis method of the SAPO-11 molecular sieve.
Background
SAPO-11 molecular sieve has good isomerization catalytic activity, and has been widely studied in the petrochemical fields of gasoline modification, diesel dewaxing and the like. The SAPO-11 molecular sieve has a one-dimensional straight pore channel structure, normal paraffin can generate isomerization reaction at the pore opening position on the outer surface of the crystal grain to generate isomeric hydrocarbon, and the SAPO-11 molecular sieve has mild acid property, is not easy to cause the isomeric hydrocarbon to generate cracking reaction, and can improve the yield of the isomeric hydrocarbon.
The common synthesis means of the SAPO-11 molecular sieve is a hydrothermal synthesis method, and the vapor self-generation pressure is high under the high-temperature condition (generally greater than 180 ℃), which puts higher quality requirements on synthesis equipment and increases the equipment cost; in addition, the high-temperature synthesis method tends to cause the aggregation phenomenon of small grains, the particle size of the formed SAPO-11 is large, the external specific surface exposure rate is low, and the isomerization reaction activity is reduced. Hydroxyl free radicals can effectively promote nucleation of the molecular sieve and accelerate the growth process of the molecular sieve, most researchers promote generation of the hydroxyl free radicals by introducing ultraviolet illumination, peroxide and seed ball milling treatment means into a synthesis system, and mild and rapid molecular sieve synthesis routes are realized, but the complexity of the molecular sieve synthesis process is inevitably improved by the existing method. Aiming at the defects of the method, the invention provides a novel method for quickly synthesizing the SAPO-11 molecular sieve by utilizing hydroxyl free radicals, so as to overcome various technical problems in the conventional hydrothermal synthesis method.
Disclosure of Invention
In order to solve the technical problems of complex synthesis method and high synthesis component of the SAPO-11 molecular sieve in the prior art, the invention provides a normal-pressure synthesis method of the SAPO-11 molecular sieve.
In order to solve the technical problems, the invention adopts the following technical scheme:
a normal pressure synthesis method of an SAPO-11 molecular sieve is characterized in that water, an aluminum source, a phosphorus source, organic amine, a silicon source and a carbon material are sequentially added into a container according to a specific molar ratio and stirred to prepare sol, and the sol is heated and crystallized under the microwave condition to obtain the molecular sieve SAPO-11; the water and the aluminum source (Al)2O3Meter)Phosphorus source (as P)2O5Calculated as SiO), organic amine, silicon source2Calculated by the formula, the molar ratio of the carbon material to the carbon material is (60-120):1.0:1.0: (1.1-1.4): 0.2-1.0: (0.01-0.50).
In the present invention, the inventors add seeds and ultra low concentration carbon materials to the hydrothermal system, replacing the conventional oven heating method with microwave heating. The carbon material is added into a molecular sieve synthesis system as a mesoporous template, the carbon material is removed through high-temperature calcination, and a mesoporous-macroporous structure is left in a molecular sieve product, so that the diffusion resistance of a macromolecular reactant/product in micropores of the SAPO-11 molecular sieve can be reduced. The inventor initially tries to induce air to generate hydroxyl radicals under microwave conditions to remarkably accelerate the nucleation of the zeolite molecular sieve by using a carbon material as a catalyst, but the inventor finds that the method finally leads to the nonsynthesizing of the SAPO-11 molecular sieve, and the inventor abandons the final idea even once, but as the experiment progresses, the inventor surprisingly finds that the finished SAPO-11 molecular sieve can be finally synthesized by skillfully adjusting the proportion content of the carbon material. The method adopts a low-proportion carbon material combined with a microwave condition, uses the carbon material as a mesoporous template agent, endows a molecular sieve with a hierarchical pore structure, reduces the diffusion resistance of a macromolecular reactant/product in micropores of the SAPO-11 molecular sieve, simultaneously uses the low-proportion carbon material as a catalyst under the microwave condition on the premise of not increasing the complexity of a synthesis process, induces air to generate hydroxyl free radicals, can regulate the concentration of the hydroxyl free radicals, enables the hydroxyl free radicals to be smoothly synthesized into the molecular sieve SAPO-11, reduces the reaction energy barrier, shortens the synthesis induction period of the molecular sieve, and remarkably accelerates the nucleation of the zeolite molecular sieve; the inventor guesses that the concentration of the hydroxyl radicals is higher probably due to the excessively high carbon material feeding, but the self-assembly process of the structural unit is influenced, and the molecular sieve product cannot be synthesized.
The crystallized product provided by the invention needs to be subjected to subsequent treatment, such as washing with deionized water, drying, roasting and the like, so that the molecular sieve SAPO-11 can be obtained, and more preferably, the mass ratio of the deionized water to the crystallized product for washing is 2-7: 1; the drying temperature is 80-100 ℃, and the drying time is 6-10 h; the roasting temperature is 450-650 ℃, and the roasting time is 4-8 h.
Preferably, the inventor adds a seed crystal to a hydrothermal system to cooperate with a carbon material, so that the synthesis induction period of the zeolite molecular sieve is further shortened, and the generation of mixed crystals is further inhibited, wherein the seed crystal can be SAPO-11 molecular sieve raw powder, the seed crystal is added in the preparation process of the sol, and the water and the aluminum source (Al is used as Al)2O3Calculated as P), a source of phosphorus (calculated as P)2O5Calculated as SiO), organic amine, silicon source2Calculated), the molar ratio of the seed crystal to the carbon material is (60-120):1.0:1.0: (1.1-1.4): 0.2-1.0: (0.03-0.30): 0.01-0.50.
The raw materials of the invention can adopt materials commonly used in the field, and preferably, the aluminum source can be one or two of pseudoboehmite or aluminum isopropoxide; the phosphorus source can be phosphoric acid; the organic amine can be one or two of di-n-propylamine and diisopropylamine; the silicon source is acidic silica sol; the carbon material can be one or more of biochar, activated carbon, graphene oxide and acetylene black.
Preferably, the stirring time is 2-8 h; the crystallization temperature is 80-100 ℃, and the crystallization time is 4-24 h.
The water can be deionized water or other water commonly used in the field, and preferably, the microwave power under the microwave condition is 200- & 1000W.
The invention provides a normal-pressure synthesis method of an SAPO-11 molecular sieve, which can realize the synthesis of the SAPO-11 molecular sieve under the conditions of low temperature and normal pressure. It is worth mentioning that the ultra-low concentration carbon material used in the invention can be used as a template agent to endow the molecular sieve with a graded pore structure and can also be used as a catalyst to induce air to generate hydroxyl radicals, and the concentration of the hydroxyl radicals is regulated so that the molecular sieve SAPO-11 is successfully synthesized, the reaction energy barrier is reduced, the nucleation of the zeolite molecular sieve is remarkably accelerated, and the molecular sieve synthesis induction period is shortened; in addition, the synthesis method provided by the invention is mild, and can effectively avoid the small crystal grain aggregation phenomenon caused by the molecular sieve SAPO-11 brought by the conventional hydrothermal synthesis method, and the molecular sieve SAPO-11 obtained by the normal-pressure synthesis method can effectively inhibit the small crystal grain aggregation phenomenon, so that the external specific surface exposure rate of the molecular sieve SAPO-11 is high, and the isomerization reaction activity can be further improved.
Drawings
FIG. 1 is an XRD spectrum of SAPO-11 molecular sieve provided by example 1 of the invention;
FIG. 2 is an XRD spectrum of SAPO-11 molecular sieve provided by example 2 of the invention;
FIG. 3 is an SEM image of a SAPO-11 molecular sieve provided by example 2 of the invention;
FIG. 4 is an XRD spectrum of a product of synthesis of a different carbon material of comparative example 1 of the present invention;
FIG. 5 is an XRD spectrum of a synthesized product of comparative example 2 of the present invention.
Detailed Description
The invention discloses a normal pressure synthesis method of SAPO-11 molecular sieve, which can be realized by appropriately improving process parameters by the technical personnel in the field by referring to the content. It is expressly intended that all such similar substitutes and modifications which would be obvious to those skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The following detailed description of the invention refers to specific embodiments thereof for better understanding by those skilled in the art.
Example 1
Deionized water and boehmite (with Al)2O3Calculated), phosphoric acid (in terms of P)2O5Calculated), organic amine di-n-propylamine, silica sol and biochar are sequentially added into a beaker according to the molar ratio of 90:1.0:1.0:1.1:0.4:0.10, the mixture is stirred for 8 hours to obtain a crystallization precursor, the obtained crystallization precursor is transferred into a crystallization kettle, and crystallization is carried out at the temperature of 100 ℃ for 8 hours under the condition that the microwave power is 600w (the operation pressure is 10100pa) to obtain a crystallization product; by mass ofWashing and filtering the crystallized product with deionized water of 4 times, drying at 100 ℃ for 6h, roasting at 650 ℃ for 8h, carrying out X-ray diffraction on the SAPO-11 molecular sieve with the AE L structure, analyzing the diffraction pattern XRD of the molecular sieve, and particularly showing in figure 1, wherein the synthesized product has the characteristic diffraction peak of the SAPO-11 molecular sieve as can be seen in figure 1.
Example 2
Deionized water and boehmite (with Al)2O3Calculated), phosphoric acid (in terms of P)2O5Calculated), organic amine di-n-propylamine and diisopropylamine, silica sol, seed crystal SAPO-11 molecular sieve raw powder and biochar are sequentially added into a beaker according to the molar ratio of 90:1.0:1.0:1.1:0.4:0.03:0.20, wherein the organic amine is a mixture of the di-n-propylamine and the diisopropylamine, the mass ratio of the organic amine to the diisopropylamine is 50: 50%, a crystallization precursor is obtained after the solution is fully stirred for 6 hours, the crystallization precursor is transferred into a crystallization kettle, and the crystallization product is obtained after crystallization is carried out for 12 hours at 90 ℃ under the condition that the microwave power is 400w (the operation pressure is 10000 pa); and (3) washing and filtering the crystallized product by using deionized water with the mass 4 times that of the crystallized product, drying the crystallized product at 90 ℃ for 8 hours, roasting the crystallized product at 550 ℃ for 6 hours, carrying out X-ray diffraction on the obtained SAPO-11 molecular sieve, analyzing the diffraction pattern XRD of the obtained SAPO-11 molecular sieve, and showing in detail in figure 2 that the synthesized product has the characteristic diffraction peak of the SAPO-11 molecular sieve.
The shape of the obtained SAPO-11 molecular sieve sample is observed by a scanning electron microscope, an SEM picture of the SAPO-11 molecular sieve sample is shown in detail in figure 3, and as can be seen in figure 3, the SAPO-11 is in irregular blocky particles, and the aggregation phenomenon of small particles is well inhibited by the synthesis method adopted by the invention.
Example 3
Deionized water and aluminum isopropoxide (as Al)2O3Calculated), phosphoric acid (in terms of P)2O5Calculated), diisopropylamine, silica sol, seed crystal SAPO-11 molecular sieve raw powder, acetylene black and activated carbon mixture are sequentially added into a beaker according to the molar ratio of 60:1.0:1.0:1.1:0.2:0.03:0.01, the solution is fully stirred for 2 hours to obtain a crystallization precursor, the crystallization precursor is transferred into a crystallization kettle, and crystallization is carried out at the temperature of 80 ℃ for 4 hours under the condition that the microwave power is 200w (the operating pressure is 10000pa) to obtain the productTo crystallize the product; and washing and filtering the crystallized product by using deionized water with the mass 2 times that of the crystallized product, drying the crystallized product at 80 ℃ for 6 hours, and roasting the crystallized product at 450 ℃ for 4 hours to obtain the SAPO-11 molecular sieve.
Example 4
Deionized water and aluminum isopropoxide (as Al)2O3Calculated), phosphoric acid (in terms of P)2O5Calculated), di-n-propylamine, silica sol, seed crystal SAPO-11 molecular sieve raw powder and a mixture of graphene and graphene oxide are sequentially added into a beaker according to the molar ratio of 120:1.0:1.0:1.4:1.0:0.3:0.5, the solution is fully stirred for 8 hours to obtain a crystallization precursor, the crystallization precursor is transferred into a crystallization kettle, and crystallization is carried out at 100 ℃ for 24 hours under the condition that the microwave power is 1000w (the operating pressure is 10000pa) to obtain a crystallization product; and washing and filtering the crystallized product by deionized water with the mass 7 times that of the crystallized product, drying the crystallized product at 100 ℃ for 10 hours, and roasting the crystallized product at 450 ℃ for 8 hours to obtain the SAPO-11 molecular sieve.
Example 5
Deionized water and aluminum isopropoxide (as Al)2O3Calculated), phosphoric acid (in terms of P)2O5Calculated), di-n-propylamine, silica sol, seed crystal SAPO-11 molecular sieve raw powder and biochar mixture carbon are sequentially added into a beaker according to the molar ratio of 120:1.0:1.0:1.4:1.0:0.3:0.08, the solution is fully stirred for 8 hours to obtain a crystallization precursor, the crystallization precursor is transferred into a crystallization kettle, and crystallization is carried out at 90 ℃ for 10 hours (the operating pressure is 10000pa) under the condition that the microwave power is 600w to obtain a crystallization product; and washing and filtering the crystallized product by using deionized water with the mass 5 times that of the crystallized product, drying the crystallized product at 90 ℃ for 8 hours, and roasting the crystallized product at 550 ℃ for 6 hours to obtain the SAPO-11 molecular sieve.
Comparative example 1
Sequentially adding deionized water, boehmite (calculated by Al2O 3), phosphoric acid (calculated by P2O 5), organic amine di-n-propylamine, diisopropylamine, silica sol, seed crystal (SAPO-11 molecular sieve) and biochar (or graphene, activated carbon or acetylene black) into a beaker according to the molar ratio of 90:1.0:1.0:1.1:0.4:0.03:2.0, wherein the organic amine is a mixture of the di-n-propylamine and the diisopropylamine, the mass ratio of the two in the mixture is 50%: 50%, fully stirring the solution for 6h to obtain a crystallization precursor, transferring the crystallization precursor into a crystallization kettle, and crystallizing at 90 ℃ for 12h under the condition that the microwave power is 400w (the operating pressure is 10000pa) to obtain a crystallization product; washing and filtering the crystallized product by deionized water with the mass 4 times that of the crystallized product, drying the crystallized product for 8 hours at the temperature of 90 ℃, roasting the crystallized product for 6 hours at the temperature of 550 ℃, carrying out X-ray diffraction on the obtained product, analyzing the diffraction pattern XRD of the product, and particularly showing in figure 4 and figure 4, wherein the bulge peaks attributed to silicon oxide and aluminum oxide prove that the SAPO-11 molecular sieve cannot be prepared under the condition of high carbon material content; the inventor guesses that the concentration of the hydroxyl radicals is higher probably due to the excessively high carbon material feeding, but the self-assembly process of the structural unit is influenced, and the molecular sieve product cannot be synthesized.
Comparative example 2
Deionized water and boehmite (with Al)2O3Calculated), phosphoric acid (in terms of P)2O5The method comprises the following steps of sequentially adding organic amine di-n-propylamine and diisopropylamine, silica sol and seed crystal (SAPO-11 molecular sieve) into a beaker according to the molar ratio of 90:1.0:1.0:1.1:0.4:0.03, wherein the organic amine is a mixture of di-n-propylamine and diisopropylamine, the mass ratio of the two is 50: 50%, fully stirring the solution for 6 hours to obtain a crystallization precursor, transferring the crystallization precursor into a crystallization kettle, crystallizing the crystallization precursor for 24 hours at 90 ℃ (the operating pressure is 10000pa) under the condition that the microwave power is 400w to obtain a crystallization product, washing and filtering the crystallization product by deionized water with the mass being 4 times of the crystallization product, drying the crystallization product for 8 hours at 90 ℃, roasting the temperature of 550 ℃ for 6 hours, carrying out X-ray diffraction on the obtained product, analyzing the diffraction pattern XRD of the crystallization product, and showing in detail in figure 5, no AE L topological structure characteristic diffraction peak is shown, which shows that the SAPO-11 molecular sieve cannot be synthesized by an air method under the condition, the hydroxyl group cannot be smoothly regulated and the free radical SAPO-11 molecular sieve cannot be induced.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A normal pressure synthesis method of an SAPO-11 molecular sieve is characterized in that water, an aluminum source, a phosphorus source, organic amine, a silicon source and a carbon material are sequentially added into a container according to a specific molar ratio and stirred to prepare sol, and the sol is heated and crystallized under the microwave condition to obtain the molecular sieve SAPO-11;
the water and the aluminum source (Al)2O3Calculated as P), a source of phosphorus (calculated as P)2O5Calculated as SiO), organic amine, silicon source2Calculated by the formula, the molar ratio of the carbon material to the carbon material is (60-120):1.0:1.0: (1.1-1.4): 0.2-1.0: (0.01-0.50).
2. The atmospheric synthesis method of claim 1, wherein the crystallized product is washed with deionized water, dried and calcined to obtain molecular sieve SAPO-11.
3. The atmospheric pressure synthesis method according to claim 1 or 2, wherein a seed crystal is added during the preparation of the sol, and the water and the aluminum source (Al) are used as the source2O3Calculated as P), a source of phosphorus (calculated as P)2O5Calculated as SiO), organic amine, silicon source2Calculated), the molar ratio of the seed crystal to the carbon material is (60-120) to 1.0:1.0 (1.1-1.4) to (0.2-1.0) to (0.03-0.30) to (0.01-0.50); the seed crystal is SAPO-11 molecular sieve raw powder.
4. The atmospheric synthesis method according to claim 1, 2 or 3, wherein the aluminum source is one or both of pseudoboehmite and aluminum isopropoxide; the phosphorus source is phosphoric acid; the organic amine is one or two of di-n-propylamine and diisopropylamine; the silicon source is acidic silica sol.
5. The normal-pressure synthesis method according to claim 1, 2 or 3, wherein the carbon material is one or more of biochar, activated carbon, graphene oxide and acetylene black.
6. The atmospheric synthesis method according to claim 1, wherein the stirring time is 2-8 h; the crystallization temperature is 80-100 ℃, and the crystallization time is 4-24 h.
7. The atmospheric synthesis method as defined in claim 1, wherein the water is deionized water, and the microwave power under the microwave condition is 200-1000W.
8. The atmospheric synthesis method according to claim 2, wherein the drying temperature is 80-100 ℃, and the drying time is 6-10 h.
9. The atmospheric synthesis method as defined in claim 2, wherein the calcination temperature is 450-650 ℃, and the calcination time is 4-8 h.
10. The atmospheric synthesis method according to claim 2, wherein the mass ratio of the washing deionized water to the crystallized product is 2-7: 1.
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