CN114524448B - Preparation method of nano alumina based on carbon neutralization - Google Patents

Preparation method of nano alumina based on carbon neutralization Download PDF

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CN114524448B
CN114524448B CN202210220030.8A CN202210220030A CN114524448B CN 114524448 B CN114524448 B CN 114524448B CN 202210220030 A CN202210220030 A CN 202210220030A CN 114524448 B CN114524448 B CN 114524448B
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reaction
kettle
nano alumina
nano
aluminate
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CN114524448A (en
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丁建飞
于盛
王蕾蕾
张恽笛
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Yancheng Institute of Technology
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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
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
    • C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
    • C01F7/142—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent with carbon dioxide
    • 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
    • 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
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution
    • 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
    • C01P2006/80—Compositional purity
    • 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
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention relates to a preparation method of nano alumina based on carbon neutralization, belonging to the technical field of nano material preparation. Adding meta-aluminate and deionized water into a supercritical reaction kettle, stirring and mixing uniformly at room temperature, then introducing carbon dioxide gas into the reaction kettle to ensure that the pressure in the kettle is 7-10 MPa, heating for reaction, and introducing nitrogen to ensure that the pressure in the kettle is kept at 7-10 MPa in the reaction process; filtering the reaction product, washing with deionized water until the pH value of the filtrate is 7.0, and drying and roasting the solid product to obtain the product. The method can effectively consume carbon dioxide, plays a role of carbon neutralization, has the advantages of few raw materials, short reaction time, no need of a template agent, easy separation of products, small grain size, uniform distribution, rich pore channels, large specific surface area, large total acid quantity and high yield of the prepared nano alumina.

Description

Preparation method of nano alumina based on carbon neutralization
Technical Field
The invention relates to a preparation method of nano alumina based on carbon neutralization, belonging to the technical field of nano material preparation.
Background
Nano alumina is a very important chemical material, has the characteristics of high specific surface area, high hardness, high strength, strong oxidation resistance, good wear resistance, good insulating property, low dielectric loss and the like, and has important application in the fields of abrasive materials, coatings, rubber, structural materials, refractory materials, luminescent materials, aerospace, catalysts, carriers thereof and the like.
At present, a large number of research reports about a nano alumina preparation method are generally included in a precipitation method, a hydrothermal synthesis method, a sol-gel method and a high-temperature solid phase method, wherein the reaction time of the precipitation method is long, the specific surface area of the prepared nano alumina is small, for example, the preparation method of a nano alumina carrier with the surface rich in defect sites is disclosed in China patent application number 201710944136.1, inorganic aluminum salt and a precipitant are adopted to react for 12-48 hours at the temperature of 100-200 ℃ to prepare the nano alumina carrier, and the specific surface area of the prepared nano alumina is 150-400 m 2/g; the hydrothermal synthesis method and the sol-gel method have complex procedures, longer time and higher preparation cost, and template agents are needed, for example, china patent application No. 201711271120.5 discloses nano aluminum oxide and a preparation method thereof, wherein aluminum salt reacts with hydroxide to generate aluminum hydroxide precipitate under the condition of taking tripolyphosphate as a template additive, and the aluminum hydroxide precipitate is prepared by reacting for 1-2 hours at the temperature of 120-240 ℃; the Chinese patent application number 201711219461.8 discloses a preparation method of a nano alumina catalyst, which comprises the steps of firstly preparing gel, and then roasting the gel at high temperature; the high-temperature solid phase method has the problem of higher energy consumption, and the prepared nano alumina has the defects of smaller specific surface area, larger grain size and the like.
Therefore, how to prepare nano aluminum oxide with large specific surface area and small grain size by adopting a method with short preparation time, simple process, low energy consumption and high yield becomes a research hot spot and difficulty.
Disclosure of Invention
Aiming at the problems of complicated working procedures, long operation time, high energy consumption, high cost and the like in the existing nano aluminum oxide preparation method, the invention provides a method for preparing nano aluminum oxide, which has the advantages of simple operation, low energy consumption and short time consumption, and the prepared nano aluminum oxide is easy to separate, high in purity and yield, large in specific surface area and small in grain size.
Technical proposal
The invention adopts cheap meta-aluminate as raw material, and reacts under the condition of supercritical carbon dioxide to prepare aluminum hydroxide precursor, the aluminum hydroxide is baked to prepare nano aluminum oxide, and meanwhile, high-quality bicarbonate is obtained, and the reaction equation is as follows:
AlO2+CO2+2H2O＝Al(OH)3↓+HCO3
2Al(OH)3＝Al2O3+3H2O
The specific scheme is as follows:
A method for preparing nano alumina based on carbon neutralization, comprising the following steps:
(1) Adding meta-aluminate and deionized water into a supercritical reaction kettle, stirring and mixing uniformly at room temperature, then introducing carbon dioxide gas into the reaction kettle to ensure that the pressure in the kettle is 7-10 MPa, and heating to react to obtain a reaction product; in the reaction process, nitrogen is introduced to keep the pressure in the kettle at 7-10 MPa;
(2) Filtering the reaction product in the step (1), washing with deionized water until the pH of the filtrate is 7.0, drying the solid product, and finally roasting to obtain the nano alumina.
Further, in the step (1), the mol ratio of the meta-aluminate to the deionized water is 1 (2.0-3.2).
Further, in the step (1), the meta-aluminate is any one of lithium meta-aluminate, sodium meta-aluminate or potassium meta-aluminate.
In the step (1), the reaction temperature is 30-80 ℃ and the reaction time is 15-60 min.
In the step (2), the drying temperature is 100 ℃ and the drying time is 12-24 hours.
Further, in the step (2), the roasting temperature is 150-200 ℃ and the roasting time is 1-3 h.
The invention has the beneficial effects that:
The method for preparing the nano alumina by the supercritical carbon dioxide method is used for the first time, the method can effectively consume carbon dioxide, plays a role of carbon neutralization, has few raw materials, does not need to add a template agent, is easy to separate, ensures that aluminum hydroxide is precipitated, can be separated from solution by simple filtering operation, and has high purity; in addition, because the supercritical carbon dioxide has the advantages of high solubility and diffusion, meta-aluminate is fully contacted with carbon dioxide in a system, is quickly dissolved and reacted, has short reaction time, is favorable for forming a large amount of aluminum hydroxide precursors with small grain sizes, and has the advantages of small grain sizes, uniform distribution, rich pore channels, large specific surface area, large total acid quantity and high yield.
Drawings
FIG. 1 is an XRD pattern of nano alumina prepared in example 2 and comparative example;
FIG. 2 is an N 2 adsorption isotherm plot of nano-alumina prepared in example 2 and comparative example;
FIG. 3 is a graph showing pore size distribution of nano alumina prepared in example 2 and comparative example.
Detailed Description
The invention will be better understood by the following clear and complete description of the technical solution of the invention, taken in conjunction with the accompanying drawings and specific embodiments.
In the following examples, the purity of nano alumina was determined by: according to national standard GB/T6609.34-2009 section 34 of analytical methods and physical determination methods for aluminium oxide: calculation method of aluminum oxide content
The calculation method of the nano alumina yield comprises the following steps: according to the actual usage amount of meta-aluminate, the mass m 1 of alumina which can be obtained in theory is calculated, the mass m 2 of alumina which is obtained in practice is calculated,
Example 1
A method for preparing nano alumina based on carbon neutralization, comprising the following steps:
(1) Adding 13.2g of lithium metaaluminate and 7.2 g of deionized water into a supercritical reaction kettle, stirring at room temperature for 60min at a stirring rate of 80r/min, then introducing 4.48L of carbon dioxide gas into the reaction kettle, enabling the pressure in the kettle to be 7MPa, and heating to 30 ℃ for reaction for 60min to obtain a reaction product; in the reaction process, nitrogen is introduced to keep the pressure in the kettle at 7MPa;
(2) Filtering the reaction product of the step (1), washing with deionized water until the pH of the filtrate is 7.0, drying the solid product at 100 ℃ for 12 hours, and finally roasting at 150 ℃ for 1 hour to obtain nano-alumina, wherein the yield of the nano-alumina is 96.5% and the purity is 99.95%.
Example 2
A method for preparing nano alumina based on carbon neutralization, comprising the following steps:
(1) Adding 16.4g of sodium metaaluminate and 11.5g of deionized water into a supercritical reaction kettle, stirring at a stirring rate of 120r/min for 30min at room temperature, then introducing 8.96L of carbon dioxide gas into the reaction kettle, keeping the pressure in the kettle at 10MPa, and heating to 80 ℃ for reaction for 15min to obtain a reaction product; in the reaction process, nitrogen is introduced to keep the pressure in the kettle at 10MPa;
(2) Filtering the reaction product of the step (1), washing with deionized water until the pH of the filtrate is 7.0, drying the solid product at 100 ℃ for 24 hours, and finally roasting at 200 ℃ for 3 hours to obtain nano-alumina, wherein the yield of the nano-alumina is 99.9% and the purity is 99.99%.
Example 3
A method for preparing nano alumina based on carbon neutralization, comprising the following steps:
(1) Adding 19.6g of potassium metaaluminate and 11.5g of deionized water into a supercritical reaction kettle, stirring at room temperature for 45min at a stirring rate of 100r/min, then introducing 6.72L of carbon dioxide gas into the reaction kettle, enabling the pressure in the kettle to be 8.5MPa, and heating to 60 ℃ for reaction for 30min to obtain a reaction product; in the reaction process, nitrogen is introduced to keep the pressure in the kettle at 8.5MPa;
(2) Filtering the reaction product of the step (1), washing with deionized water until the pH of the filtrate is 7.0, drying the solid product at 100 ℃ for 24 hours, and finally roasting at 200 ℃ for 3 hours to obtain nano-alumina, wherein the yield of the nano-alumina is 99.5% and the purity is 99.96%.
Example 4
A method for preparing nano alumina based on carbon neutralization, comprising the following steps:
(1) Adding 13.2g of lithium metaaluminate and 10.8g of deionized water into a supercritical reaction kettle, stirring at a stirring rate of 120r/min for 60min at room temperature, then introducing 8.96L of carbon dioxide gas into the reaction kettle, enabling the pressure in the kettle to be 9MPa, and heating to 60 ℃ for reacting for 60min to obtain a reaction product; in the reaction process, nitrogen is introduced to keep the pressure in the kettle at 9MPa;
(2) Filtering the reaction product of the step (1), washing with deionized water until the pH of the filtrate is 7.0, drying the solid product at 100 ℃ for 12 hours, and finally roasting at 180 ℃ for 1 hour to obtain nano-alumina, wherein the yield of the nano-alumina is 99.7% and the purity is 99.98%.
Comparative example
A preparation method of nano alumina:
(1) Adding 16.4g of sodium metaaluminate and 11.5g of deionized water into a supercritical reaction kettle, stirring at room temperature for 30min at a stirring rate of 120r/min, then heating to 80 ℃, continuously introducing carbon dioxide gas with a flow rate of 0.3L/min into the reaction kettle for 30min, blowing carbon dioxide into the kettle from the bottom of the kettle through a vent pipe, discharging from the top of the kettle, keeping the pressure in the kettle at 0.1MPa,
(2) Filtering the reaction product of the step (1), washing with deionized water until the pH of the filtrate is 7.0, drying the solid product at 100 ℃ for 24 hours, and finally roasting at 200 ℃ for 3 hours to obtain nano-alumina, wherein the yield of the nano-alumina is 31.4% and the purity is 99.91%.
Fig. 1 is an XRD pattern of the nano alumina prepared in example 2 and comparative example, and as can be seen from fig. 1, the nano alumina of example 2 has significantly stronger characteristic peak intensities than that of comparative example, and has sharp characteristic peak shapes, indicating high crystallinity.
The N 2 adsorption isotherm and the pore size distribution of the nano alumina are obtained through BET characterization, and FIG. 2 is an N 2 adsorption isotherm of the nano alumina prepared in example 2 and comparative example, and as can be seen from FIG. 2, the hysteresis loop of the N 2 adsorption isotherm of the nano alumina in example 2 is obviously larger than that of the comparative example, which indicates that the quantity of mesopores in the structure is rich; fig. 3 is a graph showing pore size distribution of nano-alumina prepared in example 2 and comparative example, and it can be seen from fig. 3 that the pore size of nano-alumina in example 2 is significantly larger than that of nano-alumina in comparative example.
The nano-alumina prepared in examples 1 to 4 and comparative example was tested for the amount of strong acid on the surface, the amount of weak acid and the total acid, as well as the grain size and the specific surface area, wherein the amount of strong acid on the surface, the amount of weak acid and the total acid on the surface of nano-alumina were obtained by characterization of NH 3 -TPD, the specific surface area of nano-alumina was obtained by characterization of BET, and the grain size was obtained by characterization of SEM, and the results are shown in table 1:
TABLE 1
As can be seen from the test results of Table 1, compared with the comparative examples, the nano alumina prepared in examples 1 to 4 of the present invention has the advantages of small grain size, large specific surface area, large total acid amount, large weak acid amount, high yield, etc., because the supercritical carbon dioxide fluid has high solubility and high diffusivity, is favorable for the sufficient and rapid contact and reaction between reactants, and the product has high dispersibility, avoids agglomeration phenomenon between nano particles, thereby inhibiting the increase of grain size and increasing the number of acid active sites exposed on the surface. In the method of introducing carbon dioxide under normal pressure, the solubility of the carbon dioxide in water is low, and the normal pressure carbon dioxide gas has no solubility to meta-aluminate, so the reaction difficulty is high, and the product yield is low.

Claims (4)

1. The preparation method of the nano alumina based on carbon neutralization is characterized by comprising the following steps:
(1) Adding meta-aluminate and deionized water into a supercritical reaction kettle, stirring and mixing uniformly at room temperature, then introducing carbon dioxide gas into the reaction kettle to ensure that the pressure in the kettle is 7-10 MPa, and heating to react to obtain a reaction product; in the reaction process, the pressure in the kettle is kept at 7-10 MPa by introducing nitrogen;
(2) Filtering the reaction product in the step (1), washing with deionized water until the pH of the filtrate is 7.0, drying the solid product, and finally roasting to obtain nano alumina;
In the step (1), the reaction temperature is 30-80 ℃ and the reaction time is 15-60 min; in the step (2), the roasting temperature is 150-200 ℃ and the roasting time is 1-3 h.
2. The method for preparing nano alumina based on carbon neutralization according to claim 1, wherein in the step (1), the molar ratio of meta-aluminate to deionized water is 1 (2.0-3.2).
3. The method for preparing nano alumina based on carbon neutralization according to claim 1, wherein in the step (1), the meta aluminate is any one of lithium meta aluminate, sodium meta aluminate or potassium meta aluminate.
4. The method for preparing nano alumina based on carbon neutralization according to claim 1, wherein in the step (2), the drying temperature is 100 ℃ and the drying time is 12-24 hours.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1762600A (en) * 2004-10-22 2006-04-26 中国石油化工股份有限公司 A kind of method of reproducing catalyst by supercritical fluid

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1762600A (en) * 2004-10-22 2006-04-26 中国石油化工股份有限公司 A kind of method of reproducing catalyst by supercritical fluid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Assembly of γ-Alumina Nanorods via Supercritical Technology;Jing Yu et al.;CRYSTAL GROWTH&DESIGN;20120430;第2872-2876页 *

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