CN112250083B - Micro-mesoporous composite aluminum phosphate molecular sieve and preparation method thereof - Google Patents
Micro-mesoporous composite aluminum phosphate molecular sieve and preparation method thereof Download PDFInfo
- Publication number
- CN112250083B CN112250083B CN201910660535.4A CN201910660535A CN112250083B CN 112250083 B CN112250083 B CN 112250083B CN 201910660535 A CN201910660535 A CN 201910660535A CN 112250083 B CN112250083 B CN 112250083B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- micro
- aluminum phosphate
- preparation
- phosphate molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 55
- 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 55
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002028 Biomass Substances 0.000 claims abstract description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003610 charcoal Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 15
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
- 230000008025 crystallization Effects 0.000 claims abstract description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- 229940043279 diisopropylamine Drugs 0.000 claims description 4
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 4
- 229920005610 lignin Polymers 0.000 claims description 3
- 229920002488 Hemicellulose Polymers 0.000 claims description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 2
- 235000011613 Pinus brutia Nutrition 0.000 claims description 2
- 241000018646 Pinus brutia Species 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- -1 hydroxyl radicals Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 238000009996 mechanical pre-treatment Methods 0.000 description 2
- 230000002085 persistent effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
-
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a micro-mesoporous composite aluminum phosphate molecular sieve and a preparation method thereof. The preparation method comprises the following steps: pretreating a biomass raw material to obtain treated powder, and treating the treated powder at high temperature to obtain biomass charcoal; mixing pseudo-boehmite, phosphoric acid, organic amine, water, a heteroatom source and biomass, stirring, and adjusting the pH to 3.5-8.0 to obtain a crystallization precursor; and (3) carrying out hydrothermal crystallization on the crystallization precursor at the temperature of 140-200 ℃ for 30min-2h to obtain a crystallization product, washing, filtering, drying, and roasting to obtain the micro-mesoporous composite aluminum phosphate molecular sieve. The aluminum phosphate molecular sieve has a micro-mesoporous structure and has a higher specific surface area.
Description
Technical Field
The invention relates to a preparation method of a molecular sieve, in particular to a preparation method of a micro-mesoporous composite aluminum phosphate molecular sieve, belonging to the technical field of molecular sieve preparation.
Background
Hetero atoms are introduced into the framework through isomorphous substitution, so that acid catalytic activity can be endowed to the aluminum phosphate molecular sieve, and the MeAPO-11, meAPO-34, meAPO-5 molecular sieves and the like are widely applied.
MeAPO-11 molecular sieves have shown excellent reactivity in the field of direct alkane isomerization due to their suitable one-dimensional ten-membered ring structure and mild acid properties. The MeAPO-34 molecular sieve has a chabazite eight-membered ring channel structure, and shows extremely high ethylene and propylene selectivity in a methanol-to-olefin process. MeAPO-5 is a twelve-membered ring channel structure and has higher catalytic capability in alkylation and other reactions. In a heterogeneous catalytic reaction, the diffusion of reactants and products has a significant effect on the catalytic reaction. The prepared micro-mesoporous composite molecular sieve can increase the introduction of a mesoporous structure, reduce the diffusion resistance of micropores, increase the contact capacity of reactants and catalytic active sites, promote products to be separated from a catalytic phase and inhibit side reactions. The preparation of the micro-mesoporous composite molecular sieve can be realized by a method of adding a mesoporous template (such as a soft template CTAB, a hard template active carbon and a carbon nano tube). The mesoporous template is added to construct a mesoporous structure while the molecular sieve crystal is formed, however, the added mesoporous template influences the structure guiding effect of the microporous template machine on a phosphorus-oxygen tetrahedron, an aluminum-oxygen tetrahedron and a silicon-oxygen tetrahedron, and the growth speed of the molecular sieve is reduced.
Researches show that hydroxyl radicals have promotion effects on depolymerization of amorphous silicon-aluminum species and formation of Si-O-Al chemical bonds in the synthesis process of the molecular sieve, and the growth of the molecular sieve can be accelerated by increasing the concentration of the hydroxyl radicals. The introduction of hydroxyl free radicals into a synthesis system can be realized by introducing hydrogen peroxide and providing ultraviolet illumination. However, hydrogen peroxide is an explosive chemical, and ultraviolet illumination requires an additional light source, which inevitably increases the operation complexity.
Disclosure of Invention
In order to solve the above problems, the present invention aims to provide a method for preparing an aluminum phosphate molecular sieve, wherein the prepared aluminum phosphate molecular sieve has a micro-mesoporous structure and a relatively high specific surface area.
In order to achieve the technical purpose, the invention provides a preparation method of a micro-mesoporous composite aluminum phosphate molecular sieve, which comprises the following steps:
pretreating a biomass raw material to obtain treated powder, and treating the treated powder at high temperature to obtain biomass charcoal;
mixing pseudo-boehmite, phosphoric acid, organic amine, water, a heteroatom source and biomass charcoal, stirring, and adjusting the pH to 3.5-8.0 to obtain a crystallization precursor (sol); wherein the pseudoboehmite (with Al) 2 O 3 Meter): a heteroatom source: phosphoric acid (with P 2O 5 Meter): organic amine: the molar ratio of water is (0.8-1.0): (0-0.6): 1: (0.8-1.2): (50-100) pseudoboehmite (with Al) 2 O 3 Calculated) and biomass charcoal in a mass ratio of 1-500:1;
and (3) carrying out hydrothermal crystallization on the crystallization precursor at the temperature of 140-200 ℃ for 30min-2h to obtain a crystallization product, washing, filtering, drying, and roasting to obtain the micro-mesoporous composite aluminum phosphate molecular sieve.
In the preparation method, biomass carbon rich in persistent free radicals is introduced into a molecular sieve synthesis system and is used as a mesoporous template and a free radical initiating group (a molecular sieve growth promoter). After the molecular sieve is roasted, removing the biomass carbon to obtain a mesoporous structure; meanwhile, the biomass carbon is rich in persistent free radicals, so that the crystallization speed is accelerated, the crystallinity of the molecular sieve is improved, and the specific surface area is increased. Therefore, the aluminum phosphate molecular sieve with high purity, high crystallinity, high specific surface area and rich micro-mesoporous composite pore channel structure can be simply, conveniently and quickly prepared by adding the biomass carbon.
The preparation method comprises the step of preparing the biomass charcoal. Specifically, biomass raw materials are subjected to mechanical pretreatment to obtain biomass powder, and the biomass powder is subjected to high-temperature treatment to obtain biomass charcoal.
In one embodiment of the invention, the mechanical pretreatment comprises crushing, grinding, sieving or drying.
In one embodiment of the present invention, the high temperature treatment temperature may be 300 ℃ to 900 ℃. For example, the temperature of the high-temperature treatment may be 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃ or the like.
In one embodiment of the present invention, the high temperature treatment time may be 1h to 20h.
In one embodiment of the present invention, the processing atmosphere for the high temperature treatment is vacuum or an inert atmosphere. Wherein the inert atmosphere may be N 2 Or Ar.
In one embodiment of the present invention, the biomass feedstock employed may be biomass and/or biomass-based chemicals. Wherein, the biomass can be pine needles and/or corn straws, and the biomass chemicals can be one or the combination of more than two of cellulose, lignin and hemicellulose.
The preparation method of the invention comprises the step of preparing the crystallization precursor. Wherein, pseudo-boehmite, phosphoric acid, organic amine, water, heteroatom source and biomass charcoal are mixed, stirred and the pH is adjusted to 3.5-8.0 to prepare a crystallization precursor.
In one embodiment of the invention, the heteroatom source used is one or a combination of two or more of soluble compounds of Si, fe, mg, ca, zn, co, cu, ni, ti, zr, mn, Y, la, ce and hydrolysable compounds of Si, fe, mg, ca, zn, co, cu, ni, ti, zr, mn, Y, la, ce.
In the preparation method of the micro-mesoporous composite aluminum phosphate molecular sieve, organic amine is used as an organic template agent. In a specific embodiment of the present invention, the organic amine is one or a combination of two or more of di-n-butylamine, triethylamine, tri-n-propylamine, tetraethylammonium hydroxide, morpholine, di-n-propylamine, and diisopropylamine.
In one embodiment of the invention, the stirring time is 30min to 120min.
The preparation method comprises the step of carrying out hydrothermal crystallization on a crystallization precursor to obtain the micro-mesoporous composite aluminum phosphate molecular sieve.
In a specific embodiment of the invention, deionized water is used for washing, wherein the mass ratio of the deionized water to the crystallized product is 6-11:1.
in one embodiment of the invention, the drying temperature is 60-120 ℃, and the drying time is 2-12 h.
In one embodiment of the invention, the roasting temperature is 500-650 ℃, and the roasting time is 2-4 h.
The invention also provides a micro-mesoporous composite aluminum phosphate molecular sieve, wherein the micro-mesoporous composite aluminum phosphate molecular sieve is prepared by the preparation method of the micro-mesoporous composite aluminum phosphate molecular sieve. The micro-mesoporous composite aluminum phosphate molecular sieve has high crystallinity, high purity and high specific surface area (200 m) 2 /g-500m 2 /g) and micro-mesoporous composite structures.
The preparation method of the micro-mesoporous composite aluminum phosphate molecular sieve comprises the steps of firstly preparing biomass charcoal, then preparing a molecular sieve crystallization precursor rich in the biomass charcoal, and rapidly synthesizing the phosphorus aluminum molecular sieve through hydrothermal crystallization. The preparation method is simple and quick in process, and the prepared molecular sieve has the advantages of high crystallinity, high specific surface area, high purity and a micro-dielectric composite pore channel structure.
Drawings
Figure 1 is an XRD spectrum of the aluminum phosphate molecular sieve of example 1.
FIG. 2 is an SEM image of the aluminum phosphate molecular sieve of example 2.
Figure 3 is an XRD spectrum of the aluminum phosphate molecular sieve of example 3.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
This example provides a method for preparing an aluminophosphate SAPO-11 molecular sieve, comprising the steps of:
and (3) roasting the cellulose for 4 hours at 500 ℃ in an anaerobic environment, and naturally cooling to obtain biomass charcoal for subsequent use.
Pseudo-boehmite (Nicoti Henghui chemical Co., ltd., al) 2 O 3 70 wt%), phosphoric acid (analytical purity, west longa chemical corporation), silica sol (Qingdao north ocean chemical industry, al) 2 O 3 30wt percent of di-n-propylamine (chemical purity of national drug group chemical reagent company limited) and diisopropylamine (chemical purity of national drug group chemical reagent company limited) in the mass ratio of 1:1, water and biochar are mixed and stirred for 120 minutes, and then the pH value of the system is adjusted to 5.5, so as to prepare the sol. Wherein: pseudo-boehmite (with Al) 2 O 3 Meter): phosphoric acid (with P) 2 O 5 Meter): silica sol (in SiO) 2 Counting): organic amine: water molar ratio 1.0 2 O 3 Meter): the mass ratio of the biomass charcoal is 300:1.
crystallizing the obtained sol in a high-pressure crystallization kettle for 30 minutes in an oven at the temperature of 200 ℃ to obtain a crystallized product; washing and filtering with deionized water 6 times the mass of the crystallized product, drying at 100 ℃ for 4 hours, and roasting at 600 ℃ for 4 hours to obtain the SAPO-11 molecular sieve of the aluminum phosphate.
The phase structure of SAPO-11 molecular sieve of aluminum phosphate is shown in figure 1, and the specific surfaceProduct of 220m 2 (g) the mesoporous specific surface area is 120m 2 /g。
Example 2
The embodiment provides a preparation method of an aluminum phosphate LaAPO-11 molecular sieve, which comprises the following steps:
and (3) roasting the lignin for 4 hours at 400 ℃ in an anaerobic environment, and naturally cooling to obtain biomass charcoal for subsequent use.
Pseudo-boehmite (Nicotai Henghui chemical Co., ltd., al) 2 O 3 70 wt%), phosphoric acid (analytically pure by Xiong chemical Co., ltd.), diisopropylamine (chemically pure by the national drug group chemical reagents Co., ltd.), water, lanthanum nitrate (analytically pure by the national drug group chemical reagents Co., ltd.), and biomass charcoal were mixed and stirred for 100 minutes, and then the pH of the system was adjusted to 4.0 to obtain a sol. Wherein: pseudo-boehmite (with Al) 2 O 3 Counting): lanthanum nitrate (with La) 2 O 3 Counting): phosphoric acid (with P) 2 O 5 Meter): di-n-propylamine: deionized water mole ratio 1.0 2 O 3 Meter): the mass ratio of the biomass charcoal is 60:1.
heating the sol in an oven to 200 ℃ and crystallizing for 1 hour to obtain a crystallized product; washing and filtering with deionized water 11 times the mass of the crystallized product, drying at 120 ℃ for 2 hours, and roasting at 550 ℃ for 4 hours to obtain the aluminum phosphate LaAPO-11 molecular sieve.
The morphology of the LaAPO-11 molecular sieve of the aluminum phosphate of the embodiment is shown in FIG. 2, and the molecular sieve has a characteristic diffraction peak of AEL topological structure and a specific surface area of 210m 2 (g) mesoporous specific surface area 98m 2 /g。
Example 3
This example provides a method for preparing an aluminophosphate CuAPO-5 molecular sieve, comprising the steps of:
and (3) roasting the cellulose for 3 hours at 600 ℃ in an anaerobic environment, and naturally cooling to obtain biomass charcoal for subsequent use.
Pseudo-boehmite (Nicoti Henghui chemical Co., ltd., al) 2 O 3 The content is 70wt%) Phosphoric acid (analytically pure chemical company, west longu), tri-n-propylamine, water, copper nitrate (analytically pure chemical reagent company, national drug group) and biomass charcoal were mixed and stirred for 60 minutes, and then the pH of the system was adjusted to 5.0 to obtain a sol. Wherein the pseudoboehmite (with Al) 2 O 3 Meter): copper nitrate (calculated as CuO): phosphoric acid (with P) 2 O 5 Meter): tri-n-propylamine: water molar ratio 0.9 2 O 3 Meter): the mass ratio of the biomass charcoal is 100:1.
and (2) crystallizing for 1 hour in an oven at the temperature of 200 ℃ to obtain a crystallized product, washing and filtering with deionized water with the mass 8 times that of the crystallized product, drying for 12 hours at the temperature of 80 ℃, and roasting for 2 hours at the temperature of 550 ℃ to obtain the CuAPO-5 molecular sieve of the aluminum phosphate.
The CuAPO-5 molecular sieve phase structure of the aluminum phosphate of this example is shown in FIG. 3, and the specific surface area is 260m 2 (g) the mesoporous specific surface is 110m 2 /g。
Claims (10)
1. A preparation method of a micro-mesoporous composite aluminum phosphate molecular sieve comprises the following steps:
pretreating a biomass raw material to obtain treated powder, and treating the treated powder at high temperature to obtain biomass charcoal;
mixing pseudo-boehmite, phosphoric acid, organic amine, water, a heteroatom source and biomass charcoal, stirring, and adjusting the pH to 3.5-8.0 to obtain a crystallization precursor; wherein, pseudoboehmite: heteroatom source: phosphoric acid: organic amine: the molar ratio of water is (0.8-1.0): (0-0.6): 1: (0.8-1.2): (50-100), wherein the mass ratio of the pseudo-boehmite to the biomass charcoal is 1-500:1; wherein the pseudoboehmite is Al 2 O 3 Measured as P for phosphoric acid 2 O 5 Counting;
carrying out hydrothermal crystallization on the crystallization precursor at the temperature of 140-200 ℃ for 30min-2h to obtain a crystallization product, washing, filtering, drying, and roasting to obtain the micro-mesoporous composite aluminum phosphate molecular sieve;
wherein the biomass raw material is one or a combination of more than two of pine needles, corn straws, cellulose, lignin and hemicellulose, and the high-temperature treatment temperature of the treatment powder is 300-900 ℃.
2. The preparation method according to claim 1, wherein the time of the high temperature treatment is 1 to 20 hours.
3. The production method according to claim 1, wherein a processing atmosphere of the high-temperature treatment is a vacuum or an inert atmosphere.
4. The production method according to claim 1, wherein the heteroatom source is one or a combination of two or more of soluble compounds and hydrolyzable compounds of Si, fe, mg, ca, zn, co, cu, ni, ti, zr, mn, Y, la, ce.
5. The production method according to claim 1, wherein the organic amine is one or a combination of two or more of di-n-butylamine, triethylamine, tri-n-propylamine, tetraethylammonium hydroxide, morpholine, di-n-propylamine, and diisopropylamine.
6. The method according to claim 1, wherein the stirring time is 30min to 120min.
7. The preparation method of claim 1, wherein the washing is performed by using deionized water, and the mass ratio of the deionized water to the crystallized product is 6-11:1.
8. the preparation method according to claim 1, wherein the drying temperature is 60-120 ℃ and the drying time is 2-12 h.
9. The preparation method according to claim 1, wherein the roasting temperature is 500-650 ℃; the roasting time is 2-4 h.
10. A micro-mesoporous composite aluminum phosphate molecular sieve, wherein the micro-mesoporous composite aluminum phosphate molecular sieve is prepared by the preparation method of the micro-mesoporous composite aluminum phosphate molecular sieve according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910660535.4A CN112250083B (en) | 2019-07-22 | 2019-07-22 | Micro-mesoporous composite aluminum phosphate molecular sieve and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910660535.4A CN112250083B (en) | 2019-07-22 | 2019-07-22 | Micro-mesoporous composite aluminum phosphate molecular sieve and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112250083A CN112250083A (en) | 2021-01-22 |
| CN112250083B true CN112250083B (en) | 2022-12-09 |
Family
ID=74224540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910660535.4A Active CN112250083B (en) | 2019-07-22 | 2019-07-22 | Micro-mesoporous composite aluminum phosphate molecular sieve and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112250083B (en) |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864096B (en) * | 2010-05-27 | 2012-05-30 | 南京工业大学 | Organic/zeolite hybrid material and preparation method thereof |
| CN102009986B (en) * | 2010-09-29 | 2012-03-07 | 中国科学院广州能源研究所 | Method for co-production of zeolite molecular sieves, high-grade activated carbon and industrial alkali metal salt from wastes in biomass power plants |
| CN105271303B (en) * | 2015-09-17 | 2017-06-20 | 中国石油天然气集团公司 | AEL structure rare earth replaces the preparation method of aluminium phosphate molecular sieve |
| CN105110349B (en) * | 2015-09-17 | 2017-09-01 | 中国石油天然气集团公司 | The preparation method of nano-scale AEL structure molecular sieve |
| CN105174279B (en) * | 2015-09-17 | 2017-06-20 | 中国石油天然气集团公司 | The preparation method of nano-scale aluminium phosphate molecular sieve |
| CN105236445B (en) * | 2015-09-17 | 2017-06-20 | 中国石油天然气集团公司 | The microwave preparation of nano-scale aluminium phosphate molecular sieve |
| CN106115733A (en) * | 2016-06-20 | 2016-11-16 | 山东欧铂新材料有限公司 | A kind of preparation method of multi-stage porous mordenite molecular sieve |
| CN107952477B (en) * | 2016-10-14 | 2020-09-04 | 中国石油化工股份有限公司 | Application of hierarchical pore SAPO molecular sieve in methanol-to-olefin reaction |
| PL240207B1 (en) * | 2017-03-21 | 2022-02-28 | Ekologia Przedsiebiorczosc Innowacje Spolka Z Ograniczona Odpowiedzialnoscia | Method for synthesis of zeolites from ashes formed from burning and co-burning of biomass |
| CN109485065B (en) * | 2017-09-09 | 2021-03-05 | 中国石油化工股份有限公司 | Hierarchical pore molecular sieve and preparation method thereof |
| CN107934986B (en) * | 2017-11-23 | 2020-09-01 | 武汉凯迪工程技术研究总院有限公司 | Resource utilization method of biomass ash |
| CN108892152B (en) * | 2018-07-18 | 2021-06-11 | 深圳科冠华太新材料技术有限公司 | Preparation method of mesoporous SAPO-34 molecular sieve |
| CN109292792A (en) * | 2018-09-07 | 2019-02-01 | 昆明理工大学 | A kind of method that twin crystal is combined to 4A molecular sieve |
-
2019
- 2019-07-22 CN CN201910660535.4A patent/CN112250083B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112250083A (en) | 2021-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107500310B (en) | High-performance nano hierarchical pore TS-1 molecular sieve, preparation method and application thereof | |
| JP2013234109A (en) | Beta zeolite and method for producing the same | |
| CN111375442B (en) | Hierarchical pore HZSM-5 zeolite molecular sieve | |
| EP3678993B1 (en) | Synthesis of afx framework type molecular sieves | |
| CN108217665B (en) | Pure silicon nano Beta molecular sieve and preparation method thereof | |
| CN111495421A (en) | Method for directly preparing M-HZSM-5 molecular sieve | |
| CN112246274A (en) | Preparation method of binder-free multi-stage pore ZSM-5 molecular sieve catalyst | |
| CN108441245B (en) | Modified composite molecular sieve and preparation method and application thereof | |
| EP3827898A1 (en) | Catalyst for preparing ethylbenzene from ethanol and benzene, preparation therefor and use thereof | |
| CN113353954B (en) | Green synthetic stepped pore SAPO-11 molecular sieve based on natural minerals and preparation method thereof | |
| CN112250083B (en) | Micro-mesoporous composite aluminum phosphate molecular sieve and preparation method thereof | |
| CN112694100B (en) | Fe-ZSM-5 molecular sieve, preparation method and application thereof | |
| JP2018145085A (en) | Zeolite and method for producing the same | |
| KR20120091222A (en) | Method for producing mtw-type zeolite | |
| CN114572997B (en) | Mordenite molecular sieve, preparation method and application | |
| CN112591764B (en) | Single crystal aluminum-rich cascade hole HZSM-5 molecular sieve and green preparation method thereof | |
| WO2022195463A1 (en) | Synthesis of zeolites having the ferrierite structure | |
| CN110950355B (en) | Preparation method of W-SSZ-13 zeolite with high crystallinity and high hydrophobicity | |
| CN111892065A (en) | Method for preparing SAPO-34 molecular sieve by using rice hulls as silicon source | |
| CN114426293B (en) | SCM-35 molecular sieve, preparation method and application thereof | |
| CN112279270A (en) | Aluminum phosphate molecular sieve and preparation method thereof | |
| CN113426480B (en) | Preparation method and catalytic application of organic-inorganic hybrid ZOF-TS-1 molecular sieve | |
| CN113620312B (en) | Preparation method of SAPO-20 zeolite molecular sieve with high crystallinity | |
| AU2021105922A4 (en) | ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof | |
| CN112624150B (en) | Synthetic method of SAPO-34 molecular sieve, synthetic molecular sieve and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |