CN112028087B - Transition metal element doped AlPO-15 molecular sieve and preparation method thereof - Google Patents
Transition metal element doped AlPO-15 molecular sieve and preparation method thereof Download PDFInfo
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 62
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 53
- 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 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 51
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims description 39
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 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 24
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 230000035484 reaction time Effects 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 9
- 239000000084 colloidal system Substances 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 27
- 230000015572 biosynthetic process Effects 0.000 abstract description 16
- 238000003786 synthesis reaction Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 32
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- -1 polytetrafluoroethylene Polymers 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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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
- 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
- C01B37/04—Aluminophosphates [APO compounds]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- 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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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention discloses an AlPO-15 molecular sieve doped with transition metal elements and a preparation method thereof. The preparation method comprises the following steps: the preparation method comprises the following steps of taking melamine as a template agent, and adding the melamine in the preparation process to prepare the transition metal element doped AlPO-15 molecular sieve. The present invention uses melamine as a templating agent to direct the synthesis of crystals. In the synthesis process, melamine is added, and pure phase AlPO-15 crystal can be obtained under the condition that reaction parameters are changed within a certain range.
Description
Technical Field
The invention relates to the technical field of molecular sieve crystal synthesis, in particular to an AlPO-15 molecular sieve doped with transition metal elements and a preparation method thereof.
Background
The aluminum phosphate molecular sieve (AlPO-n, n refers to different types) crystal has a special pore structure and catalytic sites, and is widely applied in the fields of adsorption, separation and catalysis, wherein the special pore structure of the different types of aluminum phosphate molecular sieves can be used for adsorbing and separating specific substances, so that the synthesis of the single pure phase aluminum phosphate molecular sieve crystal is one of the key points of the current research. AlPO-15 as a special aluminum phosphate molecular sieve crystal with a diameter of about the inside
The pore structure of (2) is mainly synthesized by a hydrothermal method in a laboratory at present. However, in the prior art, the crystals can be obtained only under specific reaction conditions (such as reaction temperature, reaction time, material ratio and the like), and the change of the reaction conditions has a great influence on the types of final products, which often results in the formation of dense-phase aluminum phosphate crystals or other types of aluminum phosphate molecular sieve crystals. The phenomenon is greatly related to the types of the templates in the materials, most of known organic templates often guide synthesis of aluminum phosphate molecular sieves with various pore channel structures, so that the final product is difficult to be a single pure-phase aluminum phosphate molecular sieve, which is not only unfavorable for further research, but also plays a great role in hindering further popularization to industrial production.
In addition, in addition to the synthesis of the aluminum phosphate molecular sieve crystal only using Al, P, O as basic framework elements, the doping of the transition metal into the framework structure of the aluminum phosphate molecular sieve is also a popular research topic in the field of aluminum phosphate molecular sieves, because the doping of the transition metal leads to more stable structure of the aluminum phosphate molecular sieve, and the corresponding changes of physicochemical properties, and other special changes. However, after the transition metal element compound is introduced into the reaction material, the reaction conditions need to be changed so that the transition metal atoms can be successfully doped into the framework; in addition, the transition metal atoms with larger atomic radius are doped into the framework, so that the pore channel structure inside the molecular sieve crystal is changed, and the single pure phase of the product is influenced. Therefore, it is also important to find a preparation technique with good compatibility with transition metal elements.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a transition metal element doped AlPO-15 molecular sieve and a preparation method thereof, and aims to solve the problem that the reaction conditions in the prior art for preparing the transition metal element doped AlPO-15 crystal have great influence on the phase of a final product.
The technical scheme of the invention is as follows:
a preparation method of a transition metal element doped AlPO-15 molecular sieve is characterized in that melamine is used as a template agent, and the melamine is added in the preparation process to prepare the transition metal element doped AlPO-15 molecular sieve.
Optionally, aluminum isopropoxide is used as an aluminum source, phosphoric acid is used as a phosphorus source, deionized water is used as a solvent, and melamine is used as a template agent;
the aluminum isopropoxide is Al2O3Counting; the phosphoric acid is represented by P2O5Counting; the melamine is measured by MA; the transition metal element compound is calculated by MeO, wherein Me is a transition metal element;
in terms of mole ratio, Al2O3：P2O5：MA：MeO：H2O＝1：(0.7～1.6)：(0.36～1.5)：(0～0.36)：(600～680)。
Optionally, comprising the steps of: and uniformly mixing aluminum isopropoxide, phosphoric acid, melamine, a transition metal element compound and deionized water, and reacting to obtain the transition metal element doped AIPO-15 molecular sieve.
Optionally, the method specifically comprises the following steps:
(1) respectively adding deionized water into aluminum isopropoxide and melamine, and uniformly stirring to obtain aluminum isopropoxide colloid and melamine solution;
(2) adding a transition metal element compound into aluminum isopropoxide colloid, and uniformly stirring;
(3) adding a phosphoric acid aqueous solution into the mixture obtained in the step (2), and uniformly stirring;
(4) adding a melamine solution into the mixture obtained in the step (3), and uniformly stirring;
(5) reacting the mixture obtained in the step (4), and setting the reaction temperature and the reaction time;
(6) and after the reaction is finished, cleaning and drying to obtain the AlPO-15 molecular sieve doped with the transition metal element.
Optionally, in the step (1), the stirring time is 10 h.
Optionally, in the step (2), the stirring time is 1 h;
the transition metal element compound is cobalt chloride hexahydrate or zinc acetate dihydrate.
Optionally, in the step (3), the stirring time is 3 hours;
in the step (4), the stirring time is 2-3 h.
Optionally, in the step (5), the reaction temperature is 180-220 ℃; the reaction time is 20-55 h.
Alternatively, Al is present in a molar ratio2O3：P2O5：MA：CoO：H2O is 1: 0.9: 1.0: 0.2: 610, the reaction temperature is 200 ℃, and the reaction time is 40 h;
or, in terms of mole ratio, Al2O3：P2O5：MA：ZnO：H2O is 1: 1.15: 1.07: 0.27: 667 reaction temperatureThe reaction time was 40h at 200 ℃.
The invention relates to a transition metal element doped AlPO-15 molecular sieve, which is prepared by the preparation method of the transition metal element doped AlPO-15 molecular sieve.
Has the advantages that: compared with the known preparation technology of the transition metal element doped AlPO-15 crystal, the invention has the main improvement that melamine is used as a template agent to guide the synthesis of the crystal. The melamine is added in the synthesis process, and the pure phase AlPO-15 molecular sieve crystal can still be obtained under the condition that the reaction parameters are changed within a certain range.
Drawings
In FIG. 1, (a) is the XRD pattern of undoped AlPO-15, and (b) - (e) are the XRD patterns of the product corresponding to different amounts of cobalt chloride hexahydrate, wherein (b) is 0.2g, (c) is 0.4g, (d) is 0.6g, and (e) is 0.8 g.
FIG. 2 shows XRD standard PDF cards of undoped AlPO-15 and the XRD patterns of the products corresponding to different amounts of melamine, wherein (a)0.45g, (b)0.75g, (c)1.05g, (d)1.35g and (e)1.65 g.
Detailed Description
The invention provides an AlPO-15 molecular sieve doped with transition metal elements and a preparation method thereof, and the invention is further explained in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The inventor finds that in the prior art for preparing the transition metal element doped AlPO-15 molecular sieve crystal, although the variety of the template agents for guiding the synthesis of the transition metal element doped AlPO-15 molecular sieve crystal is large, the phase of the final product is greatly influenced by the change of the reaction conditions.
Aiming at the problem that the phase of a final product is greatly influenced by reaction conditions in the existing process of preparing the transition metal element doped AlPO-15 molecular sieve crystal, the embodiment of the invention searches a proper organic amine template agent, so that the synthesized product can still stably keep a pure-phase AlPO-15 structure after the reaction conditions are changed within a certain range.
Based on the above, the embodiment of the invention provides a preparation method of a transition metal element doped AlPO-15 molecular sieve, wherein melamine is used as a template agent, and the melamine is added in the preparation process to prepare the transition metal element doped AlPO-15 molecular sieve.
Compared with the prior preparation technology of the transition metal element doped AlPO-15 molecular sieve crystal, the embodiment of the invention is mainly improved in that melamine is used as a template agent to guide the synthesis of the crystal. Because the molecular size of melamine is similar to the size of the pore canal of the AlPO-15 molecular sieve, the melamine is taken as the template agent to be beneficial to the growth of the AlPO-15 framework structure, therefore, the melamine is added in the synthesis process, and the pure-phase AlPO-15 crystal can be obtained under the condition that the reaction parameters are changed within a certain range.
In one embodiment, aluminum isopropoxide is used as an aluminum source, phosphoric acid is used as a phosphorus source, deionized water is used as a solvent, and melamine is used as a template agent;
the aluminum isopropoxide is Al2O3Counting; the phosphoric acid is represented by P2O5Counting; the melamine is measured by MA; the transition metal element compound is calculated by MeO, wherein Me is a transition metal element, such as cobalt, zinc and the like, but not limited thereto;
in terms of mole ratio, Al2O3：P2O5：MA：MeO：H2O is 1: (0.7-1.6): (0.36-1.5): (0-0.36): (600-680). The reaction material ratio is based on the element ratio of the chemical composition of AlPO-15, fluctuates within a certain range from top to bottom, but the final product still keeps pure phase, and the phenomenon of impurity of the product caused by deviation of the chemical material ratio is avoided.
The embodiment of the invention adopts a hydrothermal synthesis method, melamine is used as a template agent, the proportion of reaction materials is changed within the range, the size and the quality of the prepared product can be regularly changed, and the product still keeps pure phase AlPO-15 monocrystal.
The embodiment of the invention takes melamine as a template agent to guide the synthesis of AlPO-15 molecular sieve crystals, and the proportion of each reaction material can be properly adjusted in the synthesis process. In the process of adjusting the reactant ratio, the following characteristics are provided:
1. product size with P2O5The increase in the ratio is first increased and then decreased, when P is2O5When the proportion is too high, obvious corrosion phenomenon can be generated on the surface of the product;
2. the size of the product is increased firstly and then reduced along with the increase of the MA ratio, and when the MA ratio is too high, twin crystals can appear in the product to cause the quality reduction of the product;
3. the size of the product is firstly increased to the maximum along with the increase of the proportion of the doped transition metal elements and then is slightly reduced, and when the proportion of the doped transition metal elements is too high, the surface of the product has defects;
4. the size of the product is firstly increased to the maximum along with the increase of the reaction temperature and then reduced, and when the reaction temperature is too high, the quality of the product is obviously reduced;
5. the product size increases to a maximum and then decreases with increasing reaction time, and when the reaction time is too long, there is an indication that the product quality is degraded.
In one embodiment, the method for preparing the transition metal element doped AlPO-15 molecular sieve comprises the following steps: uniformly mixing aluminum isopropoxide, phosphoric acid, melamine, a transition metal element compound and deionized water, and reacting to obtain the transition metal element doped AlPO-15 molecular sieve.
In one embodiment, the method for preparing the transition metal element doped AlPO-15 molecular sieve specifically comprises the following steps:
(1) respectively adding deionized water into aluminum isopropoxide and melamine, and uniformly stirring to obtain aluminum isopropoxide colloid and melamine solution;
(2) adding a transition metal element compound into aluminum isopropoxide colloid, and uniformly stirring;
(3) adding a phosphoric acid aqueous solution into the mixture obtained in the step (2), and uniformly stirring;
(4) adding a melamine solution into the mixture obtained in the step (3), and uniformly stirring;
(5) reacting the mixture obtained in the step (4), and setting the reaction temperature and the reaction time;
(6) and after the reaction is finished, cleaning and drying to obtain the AlPO-15 molecular sieve doped with the transition metal element.
In one embodiment, in step (1), the stirring time is 10 hours.
In one embodiment, in step (2), the stirring time is 1 h.
In one embodiment, in the step (2), the transition metal compound is cobalt chloride hexahydrate, zinc acetate dihydrate, or the like, but is not limited thereto.
In one embodiment, in step (3), the stirring time is 3 hours.
In one embodiment, in the step (4), the stirring time is 2-3 h.
In one embodiment, in the step (5), the reaction temperature is 180-220 ℃; the reaction time is 20-55 h.
In one embodiment, Al is present in molar ratio2O3：P2O5：MA：CoO：H2O is 1: 0.9: 1.0: 0.2: 610, the reaction temperature is 200 ℃, and the reaction time is 40 h.
In one embodiment, Al is present in molar ratio2O3：P2O5：MA：ZnO：H2O is 1: 1.15: 1.07: 0.27: 667 reaction temperature 200 deg.C, reaction time 40 h.
The following examples illustrate the sources of the reaction materials of the examples of the invention:
aluminum isopropoxide (greater than or equal to 98%, Shanghai Aladdin Biochemical technology Co., Ltd.), phosphoric acid (greater than or equal to 85%, Shanghai Linkun chemical reagent Co., Ltd.), melamine (99%, Shanghai Merlin Biochemical technology Co., Ltd.), cobalt chloride hexahydrate (98%, Shanghai Aladdin Biochemical technology Co., Ltd.), zinc acetate dihydrate (99%, Shanghai Aladdin Biochemical technology Co., Ltd.), and deionized water (prepared from a low organic matter type ultrapure water machine of Harta Master-S15 UV).
The preparation method of the transition metal element doped AlPO-15 molecular sieve provided by the embodiment of the invention can be specifically as follows:
(1) sampling aluminum isopropoxide and melamine in proportion, placing the samples in two different polytetrafluoroethylene beakers, injecting a proper amount of deionized water, placing the beakers on a magnetic stirrer, and stirring for 10 hours to respectively obtain aluminum isopropoxide colloid and melamine solution;
(2) adding a quantitative transition metal element compound (cobalt chloride hexahydrate or zinc acetate dihydrate) into aluminum isopropoxide colloid, and uniformly stirring for 1 h;
(3) adding phosphoric acid into 10ml of deionized water, stirring uniformly, then dropwise adding into the mixture obtained in the step (2), and uniformly stirring for 3 hours;
(4) dropwise adding a melamine solution into the mixture obtained in the step (3), and uniformly stirring for 2-3 h;
(5) transferring the mixture obtained in the step (4) into a polytetrafluoroethylene substrate, sealing the polytetrafluoroethylene substrate by using a stainless steel reaction kettle, placing the stainless steel reaction kettle in an oven, and setting the reaction temperature and the reaction time length;
(6) and after the reaction is finished, taking out the reaction kettle, transferring the product in the polytetrafluoroethylene substrate into a glass beaker, washing and filtering the product by using deionized water under an ultrasonic condition, and drying the product at 70-80 ℃ to obtain a solid product.
Experiments confirm that when different transition metal element compounds are used, the optimal reaction conditions are respectively as follows: (1) the proportion of the reaction materials is Al2O3:0.2CoO:0.9P2O5:1.0MA:610H2O, the reaction temperature is 200 ℃, and the reaction time is 40 h; (2) the proportion of the reaction materials is Al2O3:0.27ZnO:1.15P2O5:1.07MA:667H2And O, the reaction temperature is 200 ℃, and the reaction time is 40 h.
The embodiment of the invention provides a transition metal element doped AlPO-15 molecular sieve, wherein the transition metal element doped AlPO-15 molecular sieve is prepared by the preparation method of the transition metal element doped AlPO-15 molecular sieve.
The invention is further illustrated by the following specific examples.
Example 1
Cobalt chloride hexahydrate is taken as a variable, the dosage is changed from 0.2g to 0.8g, wherein 0.2g is taken as a change gradient, and 4 groups of experiments are performed.
Respectively placing 4.2g of aluminum isopropoxide and 1.05g of melamine in No. 1 and No. 2 polytetrafluoroethylene beakers, injecting 40ml of deionized water into the No. 1 beaker, injecting 70ml of deionized water into the No. 2 beaker, and placing the beaker on a magnetic stirrer to stir for 10 hours;
adding 0.2-0.8 g of cobalt chloride hexahydrate into a No. 1 beaker, and uniformly stirring for 1 h;
adding 2.1g of phosphoric acid into 10ml of deionized water, stirring uniformly, then dropwise adding into a No. 1 beaker, and uniformly stirring for 3 hours;
dropwise adding the melamine solution in the No. 2 beaker into the No. 1 beaker, and uniformly stirring for 2 hours;
transferring the mixture in the No. 1 beaker into a polytetrafluoroethylene substrate with the volume of 50ml, sealing the mixture by using a stainless steel reaction kettle, placing the sealed mixture in an oven, and setting the reaction temperature of 200 ℃ and the reaction time of 40 h;
and after the reaction is finished, taking out the reaction kettle, transferring the product in the polytetrafluoroethylene substrate into a glass beaker, washing and filtering the product by using deionized water under an ultrasonic condition, and drying the product at 75 ℃ to obtain a solid product.
The detailed amounts of the reactants are shown in table 1.
TABLE 1 amounts of reactants
The purity of the product was judged by phase analysis by X-ray diffraction of the prepared crystals, and the characterization results are shown in fig. 1. In FIG. 1, (a) is the XRD pattern of undoped AlPO-15, and (b) - (e) are the XRD patterns of the product corresponding to different amounts of cobalt chloride hexahydrate, wherein (b) is 0.2g, (c) is 0.4g, (d) is 0.6g, and (e) is 0.8 g. As can be seen from FIG. 1, the reaction mass cobalt chloride hexahydrate can maintain a phase-pure AlPO-15 structure under a range of varying conditions.
Example 2
Melamine was used as a variable in an amount ranging from 0.45g to 1.65g, with a gradient of 0.3g, for 5 experiments.
Respectively placing 4.2g of aluminum isopropoxide and 0.45-1.65 g of melamine in No. 1 and No. 2 polytetrafluoroethylene beakers, injecting 60ml of deionized water into the No. 1 beaker, injecting 60ml of deionized water into the No. 2 beaker, and placing the beaker on a magnetic stirrer to stir for 10 hours;
adding 0.6g of cobalt chloride hexahydrate into a No. 1 beaker, and uniformly stirring for 1 h;
adding 2.32g of phosphoric acid into 10ml of deionized water, stirring uniformly, then dropwise adding into a No. 1 beaker, and uniformly stirring for 3 hours;
dropwise adding the melamine solution in the No. 2 beaker into the No. 1 beaker, and uniformly stirring for 3 hours;
transferring the mixture in the No. 1 beaker into a polytetrafluoroethylene substrate with the volume of 50ml, sealing the mixture by using a stainless steel reaction kettle, placing the sealed mixture in an oven, and setting the reaction temperature of 200 ℃ and the reaction time of 40 h;
and after the reaction is finished, taking out the reaction kettle, transferring the product in the polytetrafluoroethylene substrate into a glass beaker, washing and filtering the product by using deionized water under an ultrasonic condition, and drying the product at 70 ℃ to obtain a solid product.
The detailed amounts of the reactants are shown in table 2.
TABLE 2 amounts of reactants
The purity of the product was judged by phase analysis by X-ray diffraction of the prepared crystals, and the characterization results are shown in fig. 2. FIG. 2 shows XRD standard PDF cards of undoped AlPO-15 and the XRD patterns of the products corresponding to different amounts of melamine, wherein (a)0.45g, (b)0.75g, (c)1.05g, (d)1.35g and (e)1.65 g. As can be seen from FIG. 2, the reaction mass melamine can maintain the pure phase AlPO-15 structure under a range of varying conditions.
In summary, the invention provides an AlPO-15 molecular sieve doped with transition metal elements and a preparation method thereof. The preparation method comprises the following steps: the preparation method comprises the following steps of taking melamine as a template agent, and adding the melamine in the preparation process to prepare the transition metal element doped AlPO-15 molecular sieve. The present invention uses melamine as a templating agent to direct the synthesis of crystals. In the synthesis process, melamine is added, and pure phase AlPO-15 crystal can be obtained under the condition that reaction parameters are changed within a certain range.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (6)
1. A preparation method of a transition metal element doped AlPO-15 molecular sieve is characterized in that a hydrothermal synthesis method is adopted, melamine is used as a template agent, and the melamine is added in the preparation process to prepare the transition metal element doped AlPO-15 molecular sieve;
aluminum isopropoxide is used as an aluminum source, phosphoric acid is used as a phosphorus source, and deionized water is used as a solvent;
the aluminum isopropoxide is Al2O3Counting; the phosphoric acid is represented by P2O5Counting; the melamine is measured by MA; the transition metal element compound is calculated by MeO, wherein Me is a transition metal element;
in terms of mole ratio, Al2O3：P2O5：MA：MeO：H2O＝1：(0.7～1.6)：(0.36～1.5)：(0～0.36)：(600～680)；
The transition metal element is cobalt or zinc;
the preparation method comprises the following steps: uniformly mixing aluminum isopropoxide, phosphoric acid, melamine, a transition metal element compound and deionized water, and reacting to obtain the transition metal element doped AlPO-15 molecular sieve;
the reaction temperature is 180-220 ℃;
the reaction time is 20-55 h.
2. The method for preparing the transition metal element-doped AlPO-15 molecular sieve according to claim 1, which comprises the following steps:
(1) respectively adding deionized water into aluminum isopropoxide and melamine, and uniformly stirring to obtain aluminum isopropoxide colloid and melamine solution;
(2) adding a transition metal element compound into aluminum isopropoxide colloid, and uniformly stirring;
(3) adding a phosphoric acid aqueous solution into the mixture obtained in the step (2), and uniformly stirring;
(4) adding a melamine solution into the mixture obtained in the step (3), and uniformly stirring;
(5) reacting the mixture obtained in the step (4), and setting the reaction temperature and the reaction time;
(6) and after the reaction is finished, cleaning and drying to obtain the AlPO-15 molecular sieve doped with the transition metal element.
3. The method for preparing transition metal element-doped AlPO-15 molecular sieve according to claim 2, wherein the stirring time in the step (1) is 10 h.
4. The method for preparing transition metal element-doped AlPO-15 molecular sieve according to claim 2, wherein in the step (2), the stirring time is 1 h;
the transition metal element compound is cobalt chloride hexahydrate or zinc acetate dihydrate.
5. The method for preparing transition metal element-doped AlPO-15 molecular sieve according to claim 2, wherein in the step (3), the stirring time is 3 h;
in the step (4), the stirring time is 2-3 h.
6. The method of claim 2, wherein the Al is in a molar ratio2O3：P2O5：MA：CoO：H2O is 1: 0.9: 1.0: 0.2: 610, the reaction temperature is 200 ℃, and the reaction time is 40 h;
or, in terms of mole ratio, Al2O3：P2O5：MA：ZnO：H2O is 1: 1.15: 1.07: 0.27: 667 reaction temperature 200 deg.C, reaction time 40 h.
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