CN115611299A - Nano fibrous boehmite and preparation method thereof - Google Patents
Nano fibrous boehmite and preparation method thereof Download PDFInfo
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- 229910001593 boehmite Inorganic materials 0.000 title claims abstract description 105
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 128
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 66
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 66
- 239000011734 sodium Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000011148 porous material Substances 0.000 claims abstract description 48
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 45
- 239000000725 suspension Substances 0.000 claims abstract description 44
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 46
- 229910052782 aluminium Inorganic materials 0.000 claims description 46
- 238000002425 crystallisation Methods 0.000 claims description 43
- 230000008025 crystallization Effects 0.000 claims description 43
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 229910019142 PO4 Inorganic materials 0.000 claims description 15
- 239000004411 aluminium Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- 239000010452 phosphate Substances 0.000 claims description 15
- 235000011128 aluminium sulphate Nutrition 0.000 claims 1
- 239000001164 aluminium sulphate Substances 0.000 claims 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- -1 polytetrafluoroethylene Polymers 0.000 description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002121 nanofiber Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006772 olefination reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- GJPYYNMJTJNYTO-UHFFFAOYSA-J sodium aluminium sulfate Chemical compound [Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJPYYNMJTJNYTO-UHFFFAOYSA-J 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
-
- 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
-
- 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
- C01P2006/14—Pore volume
-
- 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
- C01P2006/16—Pore diameter
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to the technical field of catalyst carrier preparation, in particular to nano fibrous boehmite and a preparation method thereof. The method comprises the following steps: (1) Mixing a sodium metaaluminate solution and an aluminum sulfate solution, and adding a disodium hydrogen phosphate solution into the mixed solution to obtain a suspension; (2) Crystallizing the suspension to obtain a crystallized product; (3) And sequentially carrying out suction filtration, washing and drying on the crystallized product to obtain the nano fibrous boehmite. The method can prepare the nano fibrous boehmite product with large specific surface area, large pore volume and largest but largest pore diameter, and is green, environment-friendly, simple in process and easy to industrialize.
Description
Technical Field
The invention relates to the technical field of catalyst carrier preparation, in particular to nano fibrous boehmite and a preparation method thereof.
Background
γ-Al 2 O 3 Also called active alumina, is one of the widely applied materials in heterogeneous catalyst carriers, is commonly used as a catalyst carrier for isomerization, catalytic reforming, hydrogenation and catalytic cracking in the fields of fine chemical industry, petrochemical industry and petroleum refining, and can also be directly used as a catalyst for catalyzing the dehydration of alcohol to prepare olefin and isomerization reaction. gamma-Al 2 O 3 Typically obtained by calcining boehmite at 500-800 c, and thus the preparation of boehmite is critical to the preparation of the active alumina catalyst support and its criticality.
CN102050476A discloses a method for preparing fibrous boehmite by adopting a sodium metaaluminate-carbon dioxide method, which comprises the steps of adding a surfactant into a reaction system, reacting in a hypergravity reactor, adding the surfactant in the reaction process, and adding an organic solvent in the filtering and drying processes, and heating and refluxing. The production process is complex, and the surfactant is adopted for assistance, so that the cost is increased, and on the other hand, the organic matter is difficult to completely remove to obtain the boehmite without impurities.
CN107720792A discloses a method for preparing fibrous boehmite by adopting ammonia water to precipitate an aluminum salt solution, and the specific surface area of the fibrous boehmite prepared by the method is 210-310m 2 G, but the raw materials used for its production are not environmentally friendly.
CN102653410A discloses a method for preparing boehmite with fiber morphology by an aluminum sulfate-sodium metaaluminate method, wherein a fibrous pseudo-boehmite with a diameter of 5-20nm is successfully synthesized by controlling reaction conditions and crystallization conditions, and the method is low in production cost and environment-friendly, but the specific surface area, pore volume and pore diameter of the product are small.
In summary, there is a need to develop a method for preparing fibrous boehmite, which can prepare fibrous boehmite having larger specific surface area, larger pore volume and largest possible pore diameter, and which has simple process and overcomes the problem of environmental pollution in the preparation thereof.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides the nano fibrous boehmite and the preparation method thereof, the method can prepare the nano fibrous boehmite product with large specific surface area, large pore volume and largest probable pore diameter, and the method is green and environment-friendly, has simple process and is easy for industrialization.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing nanofibrous boehmite, the method comprising:
(1) Mixing a sodium metaaluminate solution and an aluminum sulfate solution, and adding a disodium hydrogen phosphate solution into the mixed solution to obtain a suspension;
(2) Crystallizing the suspension to obtain a crystallized product;
(3) Sequentially carrying out suction filtration, washing and drying on the crystallized product to obtain nano fibrous boehmite;
wherein, in the sodium metaaluminate solution, the content of aluminum calculated by alumina is 5-10wt%, and the molar ratio of sodium to aluminum is (2-5): 1;
wherein the mass ratio of the sodium metaaluminate solution to the aluminum sulfate solution is (0.5-10): 10;
wherein the disodium hydrogen phosphate solution is used in an amount such that the molar ratio of phosphate to aluminium in the suspension is from 0.001 to 0.5:1;
wherein, in the step (2), the crystallization conditions include: the temperature is 140-240 ℃ and the time is 5-72h.
A second aspect of the invention provides a nanofibrous boehmite prepared as described above.
Through the technical scheme, the invention can obtain the following beneficial effects:
the method can prepare the nano fibrous boehmite product with large specific surface area, large pore volume and largest probable pore diameter without using a surfactant, and has the advantages of green and environment-friendly production method, simple process and easy industrialization.
Drawings
FIG. 1 is an XRD pattern of a nano-fibrous boehmite prepared according to example 3 of the invention;
FIG. 2 is a TEM image of a nano-fibrous boehmite prepared in example 3 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention is a method for preparing nanofibrous boehmite, the method comprising:
(1) Mixing a sodium metaaluminate solution and an aluminum sulfate solution, and adding a disodium hydrogen phosphate solution into the mixed solution to obtain a suspension;
(2) Crystallizing the suspension to obtain a crystallized product;
(3) Sequentially carrying out suction filtration, washing and drying on the crystallized product to obtain nano fibrous boehmite;
wherein, in the sodium metaaluminate solution, the content of aluminum calculated by alumina is 5-10wt%, and the molar ratio of sodium to aluminum is (2-5): 1;
wherein the mass ratio of the sodium metaaluminate solution to the aluminum sulfate solution is (0.5-10): 10;
wherein the disodium hydrogen phosphate solution is used in an amount such that the molar ratio of phosphate to aluminium in the suspension is from 0.001 to 0.5:1;
wherein, in the step (2), the crystallization conditions include: the temperature is 140-240 ℃, and the time is 5-72h.
It can be understood that the nanofibrous boehmite appears in a white powder state. The fibrous form is generally understood to have a root-like or needle-like structure, and is different from a sheet-like or pleated sheet-like structure.
In order to further ensure that the prepared nano fibrous boehmite has large specific surface area, large pore volume and largest maximum pore diameter, according to the present invention, it is preferable that the content of aluminum in the sodium metaaluminate solution is 6 to 7wt% in terms of alumina, and the molar ratio of sodium to aluminum is (3 to 4.8): 1.
according to the present invention, in order to further ensure that the produced nanofibrillar boehmite has a large specific surface area, a large pore volume and a maximum possible pore diameter, it is preferable that the concentration of the aluminum sulfate solution is 0.05 to 1mol/kg (for example, may be a value within a range of 0.05mol/kg, 0.1mol/kg, 0.2mol/kg, 0.3mol/kg, 0.4mol/kg, 0.5mol/kg, 0.6mol/kg, 0.7mol/kg, 0.8mol/kg, 0.9mol/kg, 1mol/kg and any two of the above), and more preferably 0.1 to 0.7mol/kg.
According to the present invention, in order to further ensure that the prepared nanofibrous boehmite has a large specific surface area, a large pore volume and a maximum probable pore diameter, it is preferable that the mass ratio of the sodium metaaluminate solution to the aluminum sulfate solution is (1-8.5): 10 (for example, 10, 5.
According to the present invention, in order to be able to further ensure that the produced nanofibrous boehmite has a large specific surface area, a large pore volume and a maximum probable pore diameter, it is preferred that the disodium hydrogen phosphate solution is used in an amount such that the molar ratio of phosphate and aluminium in the suspension is 0.005-0.2:1 (for example, can be 0.005 1, 0.01, 0.03.
According to the present invention, in order to further ensure that the prepared nanofibrous boehmite has a large specific surface area, a large pore volume and a maximum probable pore diameter, it is preferable that the mixing method comprises: the sodium metaaluminate solution and the aluminum sulfate solution are mixed in parallel flow under the condition of equal pH. It can be understood that, since the pH of the mixed solution is related to the amount ratio of the sodium metaaluminate solution to the aluminum sulfate solution, when the mass ratio of the sodium metaaluminate solution to the aluminum sulfate solution is controlled to be (0.5-10): 10, and a certain value, the pH of the mixture can be adjusted to 8.5-11 in the mixing process, and the appropriate conditions can be ensured, so that the nano fibrous boehmite with high purity can be obtained.
According to the present invention, preferably, in step (2), the crystallization conditions further include: the temperature is 160-220 ℃, and the time is 10-48h. Wherein, the device for crystallization is not particularly limited, and can be selected conventionally in the field, and preferably, the device for crystallization is a polytetrafluoroethylene reaction kettle. For example, the suspension is subjected to static crystallization or dynamic crystallization in a polytetrafluoroethylene reaction kettle. It can be understood that the dynamic crystallization is to stir the material to be crystallized in the homogeneous reactor at a certain rotation speed, which can be 10-50r/min, and other conditions are the same as those of the static crystallization.
The specific manner of the washing is not particularly limited, and for example, the washing may be 3 to 5 times with deionized water.
According to the present invention, preferably, in the step (3), the drying conditions include: the temperature is 80-160 deg.C (for example, 80 deg.C, 100 deg.C, 120 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, or any two values thereof), and the time is 8-15h (for example, 8h, 10h, 12h, 14h, 15h, or any two values thereof). More preferably, the drying conditions include: the temperature is 110-140 ℃, and the time is 10-13h.
According to a particularly preferred embodiment of the invention, the nanofibrous boehmite is prepared as follows:
(1) The method comprises the following steps of firstly carrying out equal pH parallel flow mixing on a sodium metaaluminate solution and an aluminum sulfate solution, and then adding a disodium hydrogen phosphate solution into the mixed solution to obtain a suspension;
wherein, in the sodium metaaluminate solution, the content of aluminum calculated by alumina is 6.5 to 6.7 weight percent, and the molar ratio of sodium to aluminum is (4.3 to 4.4): 1; the concentration of the aluminum sulfate solution is 0.6-0.7mol/L; the mass ratio of the sodium metaaluminate solution to the aluminum sulfate solution is (7-8.5): 10, in the mixing process, the pH of the mixed material can be 9-10; the disodium hydrogen phosphate solution is used in such an amount that the molar ratio of phosphate to aluminium in the suspension is between 0.15 and 0.2:1.
(2) Standing and crystallizing the suspension to obtain a crystallized product;
wherein the crystallization conditions include: the temperature is 210-220 ℃ and the time is 40-48h.
(3) And (3) carrying out suction filtration on the crystallized product, then washing the crystallized product for 4-5 times by using deionized water, and then drying the crystallized product for 12-13h at 135-140 ℃ to obtain the nano fibrous boehmite.
In a second aspect, the present invention provides a nanofibrous boehmite prepared as described above.
According to the present invention, it is preferable that the nanofibrous boehmite has a specific surface area of 130 to 450m 2 G (which may be 130m, for example) 2 /g、150m 2 /g、170m 2 /g、177m 2 /g、200m 2 /g、250m 2 /g、300m 2 /g、350m 2 /g、400m 2 /g、435m 2 /g、450m 2 A value in a range formed by/g and any two of the above values).
According to the present invention, it is preferable that the pore volume of the nanofibrous boehmite is 0.7 to 3.2cm 3 (e.g., it may be 0.7 cm) 3 /g、0.9cm 3 /g、1cm 3 /g、1.5cm 3 /g、2cm 3 /g、2.5cm 3 /g、3cm 3 /g、3.2cm 3 A value in a range formed by/g and any two of the above values).
According to the present invention, the maximum possible pore diameter of the nanofibrous boehmite is preferably 12 to 33nm (for example, may be a value within a range of 12nm, 15nm, 20nm, 23nm, 25nm, 28nm, 30nm, 33nm, or any two or more of these values).
The present invention will be described in detail below by way of examples.
In the following examples: sodium hydroxide, analytically pure, purchased from fuchen chemical reagent factory, tianjin;
aluminum hydroxide, analytically pure, purchased from west longa science ltd;
aluminum sulfate octadecahydrate, analytically pure, purchased from west longa science, ltd;
disodium hydrogen phosphate, analytically pure, purchased from Beijing chemical plant;
the specific surface area and pore volume parameters are measured by a BET test method; the most probable pore size parameter was measured by the BJH method.
Example 1
For explaining the nano fibrous boehmite provided by the invention and the preparation method thereof
(1) The method comprises the following steps of firstly, carrying out equal pH parallel flow mixing on a sodium metaaluminate solution and an aluminum sulfate solution (wherein the pH is = 9), and then adding a disodium hydrogen phosphate solution into the mixed solution to obtain a suspension;
wherein in the sodium metaaluminate solution, the content of aluminum calculated by alumina is 6wt%, and the molar ratio of sodium to aluminum is 3:1; the concentration of the aluminum sulfate solution is 0.1mol/kg; the mass ratio of the sodium metaaluminate solution to the aluminum sulfate solution is 1:10; the disodium hydrogen phosphate solution is used in such an amount that the molar ratio of phosphate to aluminium in the suspension is 0.01:1.
(2) Transferring the suspension to a polytetrafluoroethylene reaction kettle, and standing for crystallization to obtain a crystallized product;
wherein the crystallization temperature is 160 ℃ and the crystallization time is 10h.
(3) The crystallized product is filtered by suction, washed by deionized water for 3 times and then dried for 10 hours at 110 ℃. A white powdery boehmite was obtained. The obtained product is boehmite and does not contain any other impurities and is prepared with high purity by the characterization of XRD and the comparison with the standard JCPDSCard No.21-1307 diffraction peak card. The boehmite was found to be a nano-fibrous boehmite having a specific surface area of 341m by TEM 2 Per g, pore volume 2.01cm 3 The mode pore diameter is 20.9nm.
Example 2
For explaining the nano fibrous boehmite provided by the invention and the preparation method thereof
(1) The method comprises the following steps of firstly, carrying out equal pH parallel flow mixing on a sodium metaaluminate solution and an aluminum sulfate solution (wherein the pH is = 10), and then adding a disodium hydrogen phosphate solution into the mixed solution to obtain a suspension;
wherein, in the sodium metaaluminate solution, the content of aluminum calculated by alumina is 6.5wt%, and the molar ratio of sodium to aluminum is 4.4:1; the concentration of the aluminum sulfate solution is 0.7mol/kg; the mass ratio of the sodium metaaluminate solution to the aluminum sulfate solution is 8.5:10; the disodium hydrogen phosphate solution is used in such an amount that the molar ratio of phosphate to aluminium in the suspension is 0.2:1.
(2) Transferring the suspension to a polytetrafluoroethylene reaction kettle, and standing for crystallization to obtain a crystallized product;
wherein the crystallization temperature is 220 ℃ and the crystallization time is 48h.
(3) The crystallized product was first filtered with suction, then washed 5 times with deionized water and then dried at 140 ℃ for 13h. A white powdery boehmite was obtained. The obtained product is boehmite and does not contain any other impurities and is prepared with high purity by the characterization of XRD and the comparison with the standard JCPDSCard No.21-1307 diffraction peak card. The boehmite was found to be a nano-fibrous boehmite by TEM and had a specific surface area of 435m 2 Per g, pore volume 3.01cm 3 The mode pore diameter is 21.3nm.
Example 3
For explaining the nano fibrous boehmite provided by the invention and the preparation method thereof
(1) The method comprises the following steps of firstly, carrying out equal-pH parallel-flow mixing on a sodium metaaluminate solution and an aluminum sulfate solution (wherein the pH is = 10), and then adding a disodium hydrogen phosphate solution into the mixed solution to obtain a suspension;
wherein, in the sodium metaaluminate solution, the content of aluminum calculated by alumina is 7wt%, and the molar ratio of sodium to aluminum is 4.8:1; the concentration of the aluminum sulfate solution is 0.4mol/kg; the mass ratio of the sodium metaaluminate solution to the aluminum sulfate solution is 4:10; the disodium hydrogen phosphate solution is used in such an amount that the molar ratio of phosphate to aluminium in the suspension is 0.06:1.
(2) Transferring the suspension to a polytetrafluoroethylene reaction kettle, and standing for crystallization to obtain a crystallized product;
wherein the crystallization temperature is 200 ℃ and the crystallization time is 20h.
(3) The crystallized product was first filtered by suction, then washed 4 times with deionized water and dried at 120 ℃ for 13h. A white powdery product is obtained. The obtained product is boehmite and does not contain any other impurities and is prepared with high purity by the characterization of XRD and the comparison with the standard JCPDSCard No.21-1307 diffraction peak card. The boehmite was found to be a nano-fibrous boehmite having a specific surface area of 355m by TEM 2 Per g, pore volume 2.25cm 3 Per g, the mode pore size is 21.5nm.
Example 4
For explaining the nano fibrous boehmite provided by the invention and the preparation method thereof
(1) The method comprises the following steps of firstly, carrying out equal pH parallel flow mixing on a sodium metaaluminate solution and an aluminum sulfate solution (wherein the pH = 9.75), and then adding a disodium hydrogen phosphate solution into the mixed solution to obtain a suspension;
wherein in the sodium metaaluminate solution, the content of aluminum calculated by alumina is 6.4wt%, and the molar ratio of sodium to aluminum is 4.5:1; the concentration of the aluminum sulfate solution is 0.4mol/kg; the mass ratio of the sodium metaaluminate solution to the aluminum sulfate solution is 5:10; the disodium hydrogen phosphate solution is used in such an amount that the molar ratio of phosphate to aluminium in the suspension is 0.005:1.
(2) Transferring the suspension to a polytetrafluoroethylene reaction kettle, and standing for crystallization to obtain a crystallized product;
wherein the crystallization temperature is 160 ℃ and the crystallization time is 20h.
(3) The crystallized product is filtered by suction, washed by deionized water for 4 times and then dried for 12 hours at 120 ℃. A white powdery product is obtained. The obtained product is boehmite and does not contain any other impurities and is prepared with high purity by the characterization of XRD and the comparison with the standard JCPDSCard No.21-1307 diffraction peak card. The boehmite was found to be a nano-fibrous boehmite with a specific surface area of 304m by TEM 2 G, pore volume 1.70cm 3 The mode pore diameter is 21nm.
Example 5
For explaining the nano fibrous boehmite provided by the invention and the preparation method thereof
(1) The method comprises the following steps of firstly, carrying out equal-pH parallel-flow mixing on a sodium metaaluminate solution and an aluminum sulfate solution (wherein the pH is = 9.75), and then adding a disodium hydrogen phosphate solution into the mixed solution to obtain a suspension;
wherein in the sodium metaaluminate solution, the content of aluminum calculated by alumina is 6.4wt%, and the molar ratio of sodium to aluminum is 4.5:1; the concentration of the aluminum sulfate solution is 0.4mol/kg; the mass ratio of the sodium metaaluminate solution to the aluminum sulfate solution is 5:10; the disodium hydrogen phosphate solution is used in such an amount that the molar ratio of phosphate to aluminium in the suspension is 0.005:1.
(2) Transferring the suspension to a polytetrafluoroethylene reaction kettle, and carrying out dynamic crystallization to obtain a crystallized product;
wherein the crystallization temperature is 160 ℃ and the crystallization time is 20h.
(3) The crystallized product is filtered by suction, washed by deionized water for 4 times and then dried for 12 hours at 120 ℃. A white powdery product is obtained. The obtained product is boehmite and does not contain any other impurities and is prepared with high purity by the characterization of XRD and the comparison with the standard JCPDSCard No.21-1307 diffraction peak card. The boehmite was found to be a nano-fibrous boehmite by TEM and had a specific surface area of 232m 2 Per g, pore volume 1.32cm 3 A mode pore diameter of 30.8nm.
Example 6
For explaining the nano fibrous boehmite provided by the invention and the preparation method thereof
(1) The method comprises the following steps of firstly, carrying out equal pH parallel flow mixing on a sodium metaaluminate solution and an aluminum sulfate solution (wherein the pH is = 9), and then adding a disodium hydrogen phosphate solution into the mixed solution to obtain a suspension;
wherein, in the sodium metaaluminate solution, the content of aluminum calculated by alumina is 6.4wt%, and the molar ratio of sodium to aluminum is 4.5:1; the concentration of the aluminum sulfate solution is 0.4mol/kg; the mass ratio of the sodium metaaluminate solution to the aluminum sulfate solution is 4:10; the disodium hydrogen phosphate solution is used in such an amount that the molar ratio of phosphate to aluminium in the suspension is 0.005:1.
(2) Transferring the suspension to a polytetrafluoroethylene reaction kettle, and standing for crystallization to obtain a crystallized product;
wherein the crystallization temperature is 160 ℃ and the crystallization time is 20h.
(3) The crystallized product is filtered by suction, washed by deionized water for 4 times and then dried for 12 hours at 120 ℃. A white powdery product is obtained. The obtained product is boehmite and does not contain any other impurities and is prepared with high purity by the characterization of XRD and the comparison with the standard JCPDSCard No.21-1307 diffraction peak card. The boehmite was found to be a nano-fibrous boehmite with a specific surface area of 253m by TEM 2 Per g, pore volume 0.99cm 3 The mode pore diameter is 16nm.
Example 7
For explaining the nano fibrous boehmite provided by the invention and the preparation method thereof
(1) The method comprises the following steps of firstly, carrying out equal pH parallel flow mixing on a sodium metaaluminate solution and an aluminum sulfate solution (wherein the pH is = 9), and then adding a disodium hydrogen phosphate solution into the mixed solution to obtain a suspension;
wherein, in the sodium metaaluminate solution, the content of aluminum calculated by alumina is 5wt%, and the molar ratio of sodium to aluminum is 5:1; the concentration of the aluminum sulfate solution is 0.05mol/kg; the mass ratio of the sodium metaaluminate solution to the aluminum sulfate solution is 0.5:10; the disodium hydrogen phosphate solution is used in such an amount that the molar ratio of phosphate to aluminium in the suspension is 0.001:1.
(2) Transferring the suspension to a polytetrafluoroethylene reaction kettle, and standing for crystallization to obtain a crystallized product;
wherein the crystallization temperature is 140 ℃ and the crystallization time is 72h.
(3) And (3) carrying out suction filtration on the crystallized product, washing the crystallized product for 3 times by using deionized water, and then drying the crystallized product for 15 hours at 80 ℃. A white powdery boehmite was obtained. The obtained product is boehmite and does not contain any other impurities and is prepared with high purity by the characterization of XRD and the comparison with the standard JCPDSCard No.21-1307 diffraction peak card. The thin water was found by TEMThe alundum is nano fibrous boehmite with the specific surface area of 172m 2 Per g, pore volume 0.8cm 3 The mode pore diameter is 16nm.
Example 8
For explaining the nano fibrous boehmite provided by the invention and the preparation method thereof
(1) The method comprises the following steps of firstly, carrying out equal pH parallel flow mixing on a sodium metaaluminate solution and an aluminum sulfate solution (wherein the pH is = 10), and then adding a disodium hydrogen phosphate solution into the mixed solution to obtain a suspension;
wherein in the sodium metaaluminate solution, the content of aluminum calculated by alumina is 10wt%, and the molar ratio of sodium to aluminum is 2:1; the concentration of the aluminum sulfate solution is 1mol/kg; the mass ratio of the sodium metaaluminate solution to the aluminum sulfate solution is 10:10; the disodium hydrogen phosphate solution is used in such an amount that the molar ratio of phosphate to aluminium in the suspension is 0.5:1.
(2) Transferring the suspension to a polytetrafluoroethylene reaction kettle, and standing for crystallization to obtain a crystallized product;
wherein the crystallization temperature is 240 ℃ and the crystallization time is 5h.
(3) And (3) carrying out suction filtration on the crystallized product, washing the crystallized product for 3 times by using deionized water, and then drying the crystallized product for 8 hours at 160 ℃. A white powdery boehmite was obtained. The obtained product is boehmite and does not contain any other impurities and is prepared with high purity by the characterization of XRD and the comparison with the standard JCPDSCard No.21-1307 diffraction peak card. The boehmite was found to be a nano-fibrous boehmite with a specific surface area of 176m by TEM 2 Per g, pore volume 0.77cm 3 The mode pore diameter is 13nm.
Example 9
For explaining the nano fibrous boehmite provided by the invention and the preparation method thereof
Boehmite was prepared according to the method of example 6 except that the crystallization time was 48h.
The obtained white powdery product is characterized by XRD and compared with the standard JCPDSCard No.21-1307 diffraction peak card, and the obtained product is proved to be boehmite, anddoes not contain any other impurities, and the prepared product has high purity. The boehmite was found to be a nano-fibrous boehmite having a specific surface area of 184m by TEM 2 Per g, pore volume 0.87cm 3 The mode pore diameter is 20.7nm.
Comparative example 1
For explaining the nano fibrous boehmite provided by the invention and the preparation method thereof
(1) Performing equal-pH concurrent flow mixing on a sodium metaaluminate solution and an aluminum sulfate solution (wherein the pH is = 6), and adding a disodium hydrogen phosphate solution into the mixed solution to obtain a suspension;
wherein, in the sodium metaaluminate solution, the content of aluminum calculated by alumina is 3wt%, and the molar ratio of sodium to aluminum is 1.8:1; the concentration of the aluminum sulfate solution is 0.6mol/kg; the mass ratio of the sodium metaaluminate solution to the aluminum sulfate solution is 12:10; the disodium hydrogen phosphate solution is used in such an amount that the molar ratio of phosphate to aluminium in the suspension is 0.06:1.
(2) Transferring the suspension to a polytetrafluoroethylene reaction kettle, and standing for crystallization to obtain a crystallized product;
wherein the crystallization temperature is 200 ℃, and the crystallization time is 20h.
(3) The crystallized product is filtered by suction, washed by deionized water for 5 times and then dried for 7 hours at 70 ℃. A white powdery product is obtained. The white powdery product obtained was characterized by XRD and was apparently (H) containing 3 O)Al 3 (SO 4 ) 2 (OH) 6 Boehmite, i.e., a boehmite product that is not desired. The boehmite was found by TEM to be agglomerated lamellar particles and not a nanofiber morphology.
Comparative example 2
For explaining the nano fibrous boehmite provided by the invention and the preparation method thereof
Boehmite was prepared according to the method of example 3, except that the crystallization temperature was 80 ℃.
The white powdery product obtained was characterized by XRD and found to be boehmite. However, it was found by TEM that the boehmite was in a wrinkled sheet form and not in a nanofiber morphology.
Comparative example 3
For explaining the nano fibrous boehmite provided by the invention and the preparation method thereof
Boehmite was prepared according to the method of example 3, except that the molar ratio of sodium to aluminum in the sodium metaaluminate solution was 6:1.
the obtained white powdery product is characterized by XRD, and the obtained product is boehmite, but the boehmite is nano-flake and is not in the shape of nano-fiber by TEM.
Comparative example 4
Nanoflibrous boehmite for elucidation of reference and method for the production thereof
Boehmite was prepared according to the method of example 3, except that the sodium aluminate solution, the aluminum sulfate solution and the disodium hydrogen phosphate solution were simultaneously mixed.
The white powdery product obtained was characterized by XRD and clearly contained aluminium phosphate, and was not the desired boehmite product, which was found to be in the form of nanofibers by TEM.
Comparative example 5
Nanoflibrous boehmite for elucidation of reference and method for the production thereof
Boehmite was prepared according to the method of example 3 except that no disodium hydrogen phosphate solution was added during the synthesis. The white powdery product obtained was characterized by XRD to obtain boehmite which was found to be in the form of nanofibers with a specific surface area of 129m by TEM 2 Per g, pore volume 0.68cm 3 The mode pore diameter is 11nm.
It can be seen from the results of examples 1-9 and comparative examples 1-5 that the nano fibrous boehmite products with large specific surface area, large pore volume and largest probable pore diameter can be prepared by adopting examples 1-9 of the technical scheme of the invention without using a surfactant, and the method is green, environment-friendly, simple in process and easy to industrialize. Further, it is understood from the results of examples 6 and 9 that the structure of the nanofibrillar boehmite can be controlled by changing the crystallization time under the same other conditions.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method of preparing nano fibrous boehmite, characterized in that the method comprises:
(1) Mixing a sodium metaaluminate solution and an aluminum sulfate solution, and adding a disodium hydrogen phosphate solution into the mixed solution to obtain a suspension;
(2) Crystallizing the suspension to obtain a crystallized product;
(3) Sequentially carrying out suction filtration, washing and drying on the crystallized product to obtain nano fibrous boehmite;
wherein, in the sodium metaaluminate solution, the content of aluminum calculated by alumina is 5-10wt%, and the molar ratio of sodium to aluminum is (2-5): 1;
wherein the mass ratio of the sodium metaaluminate solution to the aluminum sulfate solution is (0.5-10): 10;
wherein the disodium hydrogen phosphate solution is used in an amount such that the molar ratio of phosphate to aluminium in the suspension is from 0.001 to 0.5:1;
wherein, in the step (2), the crystallization conditions include: the temperature is 140-240 ℃ and the time is 5-72h.
2. The process as claimed in claim 1, wherein the sodium metaaluminate solution has an aluminum content of 6-7wt% calculated as alumina and a sodium to aluminum molar ratio of (3-4.8): 1.
3. a process according to claim 1 or 2, wherein the concentration of the aluminium sulphate solution is 0.05-1mol/kg, more preferably 0.1-0.7mol/kg.
4. The process according to any one of claims 1 to 3, wherein the mass ratio of the sodium metaaluminate solution to the aluminum sulfate solution is (1-8.5): 10.
5. a process according to any one of claims 1 to 4, wherein the disodium hydrogen phosphate solution is used in an amount such that the molar ratio of phosphate to aluminium in the suspension is from 0.005 to 0.2:1.
6. the method of any of claims 1-5, wherein the method of mixing comprises: the sodium metaaluminate solution and the aluminum sulfate solution are mixed in parallel flow under the condition of equal pH.
7. The method of any one of claims 1-6, wherein the crystallization conditions further comprise: the temperature is 160-220 ℃ and the time is 10-48h.
8. The method according to any one of claims 1 to 7, wherein in step (3), the drying conditions comprise: the temperature is 80-160 ℃, and the time is 8-15h;
preferably, the drying conditions further comprise: the temperature is 110-140 ℃ and the time is 10-13h.
9. A nanofibrous boehmite prepared according to the method of any one of claims 1-8.
10. The nanofibrous boehmite of claim 9, wherein the nanofibrous boehmite has a specific surface area of 130-450m 2 /g；
Preferably, the pore volume of the nano fibrous boehmite is 0.7-3.2cm 3 /g；
Preferably, the most probable pore size of the nanofibrous boehmite is 12-33nm.
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| CN108212224A (en) * | 2017-12-06 | 2018-06-29 | 北京化工大学 | Boehmite catalyst carrier and preparation method thereof |
| CN110015673A (en) * | 2018-01-10 | 2019-07-16 | 北京化工大学 | Boehmite and preparation method thereof |
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| AU4726672A (en) * | 1972-09-29 | 1974-04-04 | Laporte Industries Ltd. | Process forthe production of alumina |
| CN102653410A (en) * | 2011-03-03 | 2012-09-05 | 中国石油天然气股份有限公司 | Method for preparing fibriform boehmite |
| CN102910654A (en) * | 2012-11-08 | 2013-02-06 | 北京化工大学 | Preparation method of fibrous boehmite with large specific surface area and large pore area |
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