CN113277530B - Niobium-doped AlPO-31 molecular sieve crystal and preparation method thereof - Google Patents
Niobium-doped AlPO-31 molecular sieve crystal and preparation method thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 66
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 59
- 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 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 36
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010955 niobium Substances 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- XZLABTOOVBNJCD-UHFFFAOYSA-D O.[Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound O.[Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XZLABTOOVBNJCD-UHFFFAOYSA-D 0.000 claims abstract description 18
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 18
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 18
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 description 13
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000007704 transition Effects 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
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/065—Aluminophosphates containing other elements, e.g. metals, boron the other elements being metals only
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- 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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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a niobium-doped AlPO-31 molecular sieve crystal and a preparation method thereof, wherein dipropylamine is used as a template agent, aluminum isopropoxide is used as an aluminum source, niobium oxalate hydrate is used as a niobium source, phosphoric acid is used as a phosphorus source, and deionized water is used as a solvent, and the dipropylamine, the aluminum isopropoxide, the niobium oxalate hydrate, the phosphoric acid and the deionized water are uniformly mixed for hydrothermal reaction to obtain the niobium-doped AlPO-31 molecular sieve crystal. The invention uses dipropylamine as a template agent to guide the synthesis of the crystal, and prepares the pure-phase niobium-doped AlPO-31 molecular sieve crystal.
Description
Technical Field
The invention relates to the field of molecular sieves, in particular to a niobium-doped AlPO-31 molecular sieve crystal and a preparation method thereof.
Background
The aluminum phosphate molecular sieve (AlPO-n, n refers to different types) crystal has special pore channel structure and catalytic sites, and is widely applied to the fields of adsorption, separation and catalysis, wherein the special pore channel structure of the aluminum phosphate molecular sieve with different types can be used for adsorbing and separating specific substances. Therefore, the synthesis of single phase, pure aluminum phosphate molecular sieve crystals is one of the major points of current research.
AlPO-31 is used as a special aluminum phosphate molecular sieve crystal, and is mainly synthesized by a hydrothermal method in a laboratory at present. However, in the existing synthesis method, 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 doping of the transition metal can lead the structure of the aluminum phosphate molecular sieve to be more stable, and the physical and chemical properties are correspondingly changed. However, after the transition metal element 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 structure inside the molecular sieve crystal is changed, and further, the synthesis of the single pure-phase molecular sieve is difficult.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a niobium-doped AlPO-31 molecular sieve crystal and a preparation method thereof, and aims to solve the problem that the existing synthesis method is difficult to synthesize a pure-phase transition metal-doped AlPO-31 molecular sieve crystal.
The technical scheme of the invention is as follows:
a preparation method of a niobium-doped AlPO-31 molecular sieve crystal comprises the steps of uniformly mixing dipropylamine, aluminum isopropoxide, niobium oxalate hydrate, phosphoric acid and deionized water by taking dipropylamine as a template agent, aluminum isopropoxide as an aluminum source, niobium oxalate hydrate as a niobium source, phosphoric acid as a phosphorus source and deionized water as a solvent, and carrying out hydrothermal reaction to obtain the niobium-doped AlPO-31 molecular sieve crystal.
Optionally, the dipropylamine, the aluminum isopropoxide, the niobium oxalate hydrate, the phosphoric acid and the deionized water are respectively DPA and Al 2 O 3 、Nb 2 O 5 、P 2 O 5 、H 2 O, metering;
in terms of mole ratios, DPA: al (aluminum) 2 O 3 ：Nb 2 O 5 ：P 2 O 5 ：H 2 O＝(0.95～1.13)：(0.98～1.1)：(0.07～0.11)：1：(550～680)。
Optionally, the preparation method of the niobium-doped AlPO-31 molecular sieve crystal specifically comprises the following steps:
mixing aluminum isopropoxide, niobium oxalate hydrate and deionized water, and stirring for the first time to obtain a solution A;
mixing phosphoric acid and deionized water, and stirring for the second time to obtain a solution B;
adding the solution B into the solution A, and stirring for the third time to obtain a solution C;
adding dipropylamine into the solution C, and stirring for the fourth time to obtain a colloidal solution D;
and carrying out hydrothermal reaction on the colloidal solution D to obtain the niobium-doped AlPO-31 molecular sieve crystal.
Optionally, the first stirring time is 10h-15h.
Optionally, the time for the second stirring is 3min to 5min.
Optionally, the third stirring time is 3-4h.
Optionally, the fourth stirring time is 1.5-2h.
Optionally, the temperature of the hydrothermal reaction is 160-170 ℃ and the time is 50-70h.
The niobium-doped AlPO-31 molecular sieve crystal prepared by the preparation method is provided.
Optionally, the niobium doped AlPO-31 molecular sieve crystal is a pure phase.
Has the advantages that: the invention provides a niobium-doped AlPO-31 molecular sieve crystal and a preparation method thereof. Dipropylamine is used as a template agent, aluminum isopropoxide is used as an aluminum source, phosphoric acid is used as a phosphorus source, and niobium oxalate hydrate is used as a niobium source, so that the pure-phase niobium-doped AlPO-31 crystal is prepared.
Drawings
FIG. 1 is a comparison of XRD pattern of the niobium doped AlPO-31 molecular sieve crystal prepared in the example and a standard XRD card.
Detailed Description
The invention provides a niobium-doped AlPO-31 molecular sieve crystal 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 although the template agent for guiding the synthesis of AlPO-31 molecular sieve crystals in the existing preparation method of AlPO-31 molecular sieve crystals is various, the preparation of pure-phase AlPO-31 molecular sieve crystals is difficult, and a synthesis scheme of doping with transition metal niobium is not reported.
In the embodiment, aiming at the problems that although the types of the existing template agents for guiding the synthesis of the AlPO-31 molecular sieve crystal are various, the pure-phase AlPO-31 molecular sieve crystal is difficult to prepare and a synthesis scheme for doping with transition metal niobium is not reported, the pure-phase niobium-doped AlPO-31 molecular sieve crystal is prepared and obtained by searching a proper template agent under the condition that reaction parameters are changed within a certain range.
Based on the above, the embodiment of the invention provides a preparation method of a niobium-doped AlPO-31 molecular sieve crystal, wherein dipropylamine is used as a template agent, aluminum isopropoxide is used as an aluminum source, niobium oxalate hydrate is used as a niobium source, phosphoric acid is used as a phosphorus source, and deionized water is used as a solvent, and the dipropylamine, the aluminum isopropoxide, the niobium oxalate hydrate, the phosphoric acid and the deionized water are uniformly mixed to perform a hydrothermal reaction, so that the niobium-doped AlPO-31 molecular sieve crystal is obtained.
In one embodiment, the dipropylamine, the aluminum isopropoxide, the niobium oxalate hydrate, the phosphoric acid and the deionized water are respectively DPA and Al 2 O 3 、Nb 2 O 5 、P 2 O 5 、H 2 Measuring O;
in terms of mole ratios, DPA: al (Al) 2 O 3 ：Nb 2 O 5 ：P 2 O 5 ：H 2 O＝(0.95～1.13)：(0.98～1.1)：(0.07～0.11)：1：(550～680)。
In this example, the niobium-doped AlPO-31 molecular sieve crystal can be synthesized by using the above raw materials and dipropylamine as a template, with a slight ratio change.
In one embodiment, the preparation method of the niobium doped AlPO-31 molecular sieve crystal specifically comprises the following steps:
s1, mixing aluminum isopropoxide, niobium oxalate hydrate and deionized water, and stirring for the first time to obtain a solution A;
s2, mixing phosphoric acid and deionized water, and stirring for the second time to obtain a solution B;
s3, adding the solution B into the solution A, and stirring for the third time to obtain a solution C;
s4, adding dipropylamine into the solution C, and stirring for the fourth time to obtain a colloidal solution D;
and S5, carrying out hydrothermal reaction on the colloidal solution D to obtain the niobium-doped AlPO-31 molecular sieve crystal.
In step S1, in one embodiment, the first stirring time is 10 hours.
In step S2, in one embodiment, the second stirring time is 3min to 5min.
In step S3, in one embodiment, the third stirring time is 3-4h.
In one embodiment, step S3 is specifically: and dropwise adding the solution B into the solution A, and stirring for 3-4h to obtain a solution C.
In step S4, in one embodiment, the fourth stirring time is 1.5-2h.
In an embodiment, step S4 is specifically: dropwise adding the dipropylamine into the solution C, and stirring for 1.5-2h to obtain the colloidal solution D.
In step S5, in one embodiment, the temperature of the hydrothermal reaction is 160-170 ℃ and the time is 50-70h. In the embodiment, the niobium-doped AlPO-31 molecular sieve crystal can be synthesized by adopting the raw materials and dipropylamine as a template within a certain temperature and time variation range.
In one embodiment, step S5 is specifically: carrying out hydrothermal reaction on the colloidal solution D at the temperature of 160-170 ℃ (165 ℃ for example) for 50-70h (60 h for example); and after the reaction is finished, filtering, washing and drying the hydrothermal product under an ultrasonic condition to obtain the niobium-doped AlPO-31 molecular sieve crystal.
In the embodiment of the invention, dipropylamine is used as a template to guide the synthesis of the niobium-doped AlPO-31 molecular sieve crystal, and the proportion of each reaction material is properly adjusted in the synthesis process, so that the pure-phase niobium-doped AlPO-31 molecular sieve crystal can be obtained. In the process of adjusting the proportion of the reaction materials, the following characteristics are provided:
1. the crystal is sensitive to Nb element doping, and when the Nb element is changed from less to more, a sample is converted into a pure-phase NbAlPO-31 crystal from a jelly with low crystallinity; because increasing the proportion of Nb results in a decrease in the degree of supersaturation in solution, an appropriate degree of supersaturation in solution favors the nucleation and growth of AlPO-31 crystals.
2. When the proportion of dipropylamine is increased, a hetero-crystalline phase of niobium-doped AlPO-31 molecular sieve crystals can appear. Because dipropylamine is more basic, increasing the proportion of dipropylamine causes a change in the pH of the solution. Different pH values accommodate different nucleation growth, so that when the pH is changed, additional heterocrystal phases appear in the resulting sample.
3. When the water ratio increased, the pure phase NbAlPO-31 crystals disappeared. Since too much water content makes the supersaturation of the solution too low to favour crystal nucleation and growth.
The embodiment of the invention also provides the niobium-doped AlPO-31 molecular sieve crystal prepared by the preparation method.
AlPO-31 is a special aluminum phosphate molecular sieve crystal with the size of the inside of the crystal being
The circular pore structure of (1).
In one embodiment, the niobium doped AlPO-31 molecular sieve crystal is phase pure.
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 Biotechnology Co., ltd.), phosphoric acid (greater than or equal to 85%, shanghai Aladdin Biotechnology Co., ltd.), dipropylamine (98%, shanghai Aladdin Biotechnology Co., ltd.), niobium oxalate hydrate (98%, shanghai Aladdin Biotechnology Co., ltd.), and deionized water (prepared from a Hetai Master-S15UV low organic matter type ultrapure water machine).
The invention is further illustrated by the following specific examples.
Examples
1 placing 4.2g of 1.02mol of aluminum isopropoxide and 1.1g of 0.1mol of niobium oxalate hydrate in a polytetrafluoroethylene beaker, adding 95ml of deionized water, and stirring for 10 hours at normal temperature to obtain a solution A.
2 mixing 2.32g of 1mol phosphoric acid with 10ml deionized water, and stirring for 3-5min to obtain a solution B.
And 3, dropwise adding the solution B into the solution A to obtain a solution C.
4 solution C was stirred at room temperature for 3 hours, and 1.02mol of dipropylamine, i.e., 1.4ml, was added to obtain solution D.
5 stirring the solution D for 2 hours, and then placing the solution into a hydrothermal reaction kettle for reaction at 165 ℃ for 60 hours; and after the reaction is finished, filtering, washing and drying the hydrothermal product under an ultrasonic condition to obtain the niobium-doped AlPO-31 molecular sieve crystal. XRD test data of the niobium doped AlPO-31 molecular sieve crystal are shown in figure 1.
In conclusion, the invention provides a niobium-doped AlPO-31 molecular sieve crystal and a preparation method thereof. Dipropylamine is used as a template agent, aluminum isopropoxide is used as an aluminum source, phosphoric acid is used as a phosphorus source, niobium oxalate hydrate is used as a niobium source, and pure-phase niobium-doped AlPO-31 crystals are prepared by regulating and controlling the proportion of the components and the reaction temperature and time.
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 (8)
1. The preparation method of the niobium-doped AlPO-31 molecular sieve crystal is characterized by uniformly mixing dipropylamine, aluminum isopropoxide, niobium oxalate hydrate, phosphoric acid and deionized water by taking dipropylamine as a template agent, aluminum isopropoxide as an aluminum source, niobium oxalate hydrate as a niobium source, and phosphoric acid as a phosphorus source and deionized water as a solvent, and carrying out hydrothermal reaction to obtain the niobium-doped AlPO-31 molecular sieve crystal;
the dipropylamine, the aluminum isopropoxide, the niobium oxalate hydrate, the phosphoric acid and the deionized water are respectively DPA and Al 2 O 3 、Nb 2 O 5 、P 2 O 5 、H 2 Measuring O;
in terms of mole ratios, DPA: al (Al) 2 O 3 ：Nb 2 O 5 ：P 2 O 5 ：H 2 O＝(0.95～1.13)：(0.98～1.1)：(0.07～0.11)：1：(550～680)；
The temperature of the hydrothermal reaction is 160-170 ℃ and the time is 50-70h.
2. The method for preparing niobium doped AlPO-31 molecular sieve crystal according to claim 1, wherein the method comprises the following steps:
mixing aluminum isopropoxide, niobium oxalate hydrate and deionized water, and stirring for the first time to obtain a solution A;
mixing phosphoric acid and deionized water, and stirring for the second time to obtain a solution B;
adding the solution B into the solution A, and stirring for the third time to obtain a solution C;
adding dipropylamine into the solution C, and stirring for the fourth time to obtain a colloidal solution D;
and carrying out hydrothermal reaction on the colloidal solution D to obtain the niobium-doped AlPO-31 molecular sieve crystal.
3. The method for preparing the niobium-doped AlPO-31 molecular sieve crystal according to claim 2, wherein the first stirring time is 10-15 h.
4. The method for preparing the niobium-doped AlPO-31 molecular sieve crystal according to claim 2, wherein the time of the second stirring is 3min to 5min.
5. The method for preparing niobium doped AlPO-31 molecular sieve crystal according to claim 2, wherein the time of the third stirring is 3-4h.
6. The method for preparing niobium-doped AlPO-31 molecular sieve crystals according to claim 2, wherein the time of the fourth stirring is 1.5 to 2h.
7. A niobium doped AlPO-31 molecular sieve crystal prepared by the preparation method of any one of claims 1 to 6.
8. The niobium doped AlPO-31 molecular sieve crystal of claim 7, wherein the niobium doped AlPO-31 molecular sieve crystal is phase pure.
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| US5888921A (en) * | 1995-10-25 | 1999-03-30 | Abb Lummus Global Inc. | Binary molecular sieves having a core and shell of different structures and compositions |
| US6498120B1 (en) * | 2000-04-26 | 2002-12-24 | Exxonmobil Chemical Patents Inc. | Rejuvenating SAPO molecular sieve with anhydrous liquid or vapor |
| US6440894B1 (en) * | 2001-06-25 | 2002-08-27 | Exxonmobil Chemical Patents, Inc. | Methods of removing halogen from non-zeolitic molecular sieve catalysts |
| US7312369B2 (en) * | 2004-04-28 | 2007-12-25 | Exxonmobil Chemical Patents Inc. | Attrition resistant molecular sieve catalyst, method of making and process for using |
| CN100376481C (en) * | 2005-04-15 | 2008-03-26 | 浙江工业大学 | Nb-containing aluminium phosphate molecular sieve composition and its prepn and application |
| CN101269822A (en) * | 2008-05-09 | 2008-09-24 | 中国石油天然气股份有限公司 | Synthesis method of aluminophosphate molecular sieve with AEL framework structure substituted by heteroatoms |
| CN102001682B (en) * | 2010-12-10 | 2012-09-05 | 黑龙江大学 | Method for synthesizing heteroatom substituted MeAPO-31 molecular sieve by microwave heating |
| CN103013556A (en) * | 2012-11-28 | 2013-04-03 | 浙江工业大学 | Method for removing trace hydrocarbon from aromatic hydrocarbon by utilizing AlPO4-5 type Al-P molecular sieve |
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