CN112978773A - High-performance aluminum oxide material and preparation method thereof - Google Patents

High-performance aluminum oxide material and preparation method thereof Download PDF

Info

Publication number
CN112978773A
CN112978773A CN202110243082.2A CN202110243082A CN112978773A CN 112978773 A CN112978773 A CN 112978773A CN 202110243082 A CN202110243082 A CN 202110243082A CN 112978773 A CN112978773 A CN 112978773A
Authority
CN
China
Prior art keywords
aluminum oxide
alumina
solid
liquid
sample
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.)
Granted
Application number
CN202110243082.2A
Other languages
Chinese (zh)
Other versions
CN112978773B (en
Inventor
常云峰
赵永生
常旭东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin Sigma Innova Technology Co ltd
Original Assignee
Tianjin Sigma Innova Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tianjin Sigma Innova Technology Co ltd filed Critical Tianjin Sigma Innova Technology Co ltd
Priority to CN202110243082.2A priority Critical patent/CN112978773B/en
Publication of CN112978773A publication Critical patent/CN112978773A/en
Application granted granted Critical
Publication of CN112978773B publication Critical patent/CN112978773B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 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
    • C01P2006/80—Compositional purity

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention relates to a high-performance aluminum oxide material and a preparation method thereof, and aims to provide a preparation method of an aluminum oxide material, which adopts a rapid and accurate structural analysis means to guide and optimize the synthesis process of aluminum oxide so as to produce a high-performance aluminum oxide product with high specific surface area, high pore volume and low sodium content. The invention controls the synthesis conditions of the alumina, and comprises the following steps: the concentration of raw material aluminum, the removal of impurities, the molar ratio of sodium hydroxide to aluminum species, the concentration, time, temperature and the like of carbon dioxide neutralization reaction are controlled comprehensively, and the preparation and production of high-purity and high-specific surface area aluminum oxide are realized by combining rapid composition and structural analysis. And the X-ray diffraction is also adopted to carry out rapid and accurate analysis on the synthetic product, so that the development pace of the material synthesis process is greatly accelerated. The alumina prepared by the method has the advantages of high specific surface area, large pore volume and low content of impurity sodium, and is a high-quality raw material of high-performance catalysts, adsorbents and high-temperature-resistant ceramic materials.

Description

High-performance aluminum oxide material and preparation method thereof
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a high-performance aluminum oxide material and a preparation method thereof.
Background
Alumina is an important industrial raw material in catalyst preparation, molecular sieve synthesis, adsorbent manufacture, coating, surfaceThe coating, the metal surface polishing agent, the high-temperature resistant material, the high-temperature ceramic, the honeycomb body carrier, the grinding tool and other fields have wide application. The requirements for the performance parameters of the alumina material are different from application to application. For the field of catalysts, the lower the sodium content in the alumina material, the higher its application value. In addition, the higher the specific surface area (BET) of the alumina material, for example, up to and even exceeding 200m2And the wider the application range of the composition, the higher the application value. As a catalyst carrier, the larger the pore volume of alumina is, more active components can be loaded, the higher the application value is, and the pore volume of the alumina is generally required to reach 0.6cm3Per gram.
In view of the variability of the soluble species of alumina, the properties of the final product are affected by a variety of chemical factors, such as the pH of the reaction solution, the impurity content of the starting materials, and the like. The effect of water is also important, which presents a significant challenge to the preparation of high surface area, high pore volume, low sodium, high performance alumina materials.
In addition, in the preparation and production of alumina, specific surface area (BET), pore volume, pore diameter, etc. of intermediate products and final products need to be measured in order to guide and control the synthesis process and production process. The specific surface area, pore volume and other data of the alumina material need to be measured by a special specific surface area analyzer. The sample is subjected to special degassing, calcination preparation and then to inert gas adsorption at low temperature, e.g. liquid nitrogen temperature, to obtain the adsorption isotherm of the gas. Nitrogen is generally used as the adsorption probe. The specific surface area and pore volume, pore size information can be obtained from the adsorption and desorption isotherms. The whole process is usually time consuming, requiring at least 6-12 hours, as shown in fig. 1 a. As a guide for controlling the production process of the alumina, the method of the specific surface area analyzer is difficult to realize rapid and timely guidance and obtain the crystal structure or microstructure information of the alumina.
Disclosure of Invention
The invention aims to provide a high-performance aluminum oxide material and a preparation method thereof aiming at various influencing factors existing in the preparation process of the aluminum oxide material. The synthesis process of the alumina is guided and optimized by adopting a rapid and accurate structural analysis means, so that a high-performance alumina product with high specific surface area, high pore volume and low sodium content is produced.
The invention adopts the following technical scheme:
a method for rapidly preparing a high-performance aluminum oxide material comprises the following steps:
(1) preparing a sodium metaaluminate solution: adding sodium hydroxide into a container filled with deionized water under the condition of stirring, and controlling the temperature of the system to be 65-82 ℃ to prepare a sodium hydroxide solution; adding aluminum hydroxide into the prepared sodium hydroxide solution, continuously stirring, and controlling the system temperature to be 90-95 ℃ until a nearly transparent liquid, namely a sodium metaaluminate solution, is obtained;
(2) removing impurities: cooling the sodium metaaluminate solution obtained in the step (1) to below 65 ℃, stopping stirring, standing, removing solid matters deposited at the bottom, and taking the obtained clear liquid as a raw material for synthesizing the aluminum oxide material;
(3) preparing aluminum oxide: diluting the clear liquid obtained in the step (2), and reacting the diluted clear liquid with mixed gas containing carbon dioxide to prepare alumina crystals, wherein the method comprises the following specific steps: transferring the diluted clear liquid into an open reactor with a gas distribution disc arranged at the bottom, introducing mixed gas containing carbon dioxide from the bottom of the reactor, obtaining uniform bubbles through the gas distribution disc, reacting the uniform bubbles with the diluted clear liquid, wherein the reaction temperature is 23-26.5 ℃, the reaction product is a white precipitate, and the reaction tail gas is discharged from the upper part of the reactor;
(4) aging of reaction products: transferring the solid-liquid mixture reacted in the step (3) into a container provided with a stirring and temperature control system for aging, wherein the aging temperature is controlled to be 65-85 ℃, the stirring speed is controlled to be 0.98-2.00 m/s at the linear speed of a stirring paddle, and the aging time is 0.8-3.2 hours;
(5) taking 50-100 ml of the mixture obtained in the step (4), carrying out centrifugal separation and washing on the mixture, wherein the centrifugal speed is 22.00-31.4 m/S in terms of linear velocity, washing the centrifugally separated solid by deionized water, and washing until the conductivity of the washing liquid is less than 50 mu S/cm, wherein the weight ratio of the washing liquid to the solid is 5-8: 1; carrying out X-ray diffraction analysis on the washed solid sample; the scanning speed is 0.001 degree/s; the 2 theta scanning range is 5-75 degrees; a copper target is used as an X-ray source, and a Bruker D8 diffractometer is adopted; a LynxEye detector is adopted; the 2 theta-48.8 DEG diffraction peak is used as the analysis for identifying and quantifying the formation of the alumina material and the formation amount thereof and is used as the basis for controlling the process control and optimizing data of the synthesis process of the alumina material;
(6) product separation: and (4) filtering and separating the solid-liquid mixture obtained in the step (4) while the solid-liquid mixture is hot to obtain a solid product, and washing the solid product by using deionized water until the conductivity of the washing liquid is less than 50 mu S/cm to obtain the final aluminum oxide material product.
Further, the stirring speed in the step (1) is 95-230 RPM.
Further, the molar ratio of the deionized water to the sodium hydroxide in the step (1) is 7-13: 1, the molar ratio of the sodium hydroxide to the aluminum hydroxide is 0.98-1.35.
Further, the standing time in the step (2) is 10-17 min.
Further, the volume percentage of carbon dioxide in the mixed gas containing carbon dioxide in the step (3) is 25-55 vol%.
Further, the air inlet speed in the step (3) is 17.4-20.9L/L of diluted clear liquid/min.
Further, the ratio of the height to the diameter of the reactor in the step (3) is 1-1.3: 1.
Further, washing in the step (5) until the conductivity of the washing liquid is less than 15 mu S/cm.
The high-performance aluminum oxide material prepared by the method has the single crystal appearance of a nearly hexagon; the purity of the aluminum oxide material is more than 99.96 percent, the sodium content is less than 250ppm, and the specific surface area is 140-289m2Per g, pore volume of 0.68-1.18cm3/g。
The invention has the beneficial effects that:
1. the invention provides a method for quickly and accurately guiding and controlling the synthesis of high-performance alumina. The method comprises the following steps of synthesizing the aluminum oxide: the concentration of raw material aluminum, the removal of impurities, the molar ratio of sodium hydroxide to aluminum species, the concentration, time, temperature and the like of carbon dioxide neutralization reaction are controlled comprehensively, and the preparation and production of high-purity and high-specific surface area aluminum oxide are realized by combining rapid composition and structural analysis. Wherein, X-ray diffraction is also adopted to carry out rapid and accurate analysis on the synthesized product, thereby greatly accelerating the development step of the material synthesis process and preparing the high-performance and high-purity aluminum oxide material as shown in b in figure 1.
2. The alumina prepared by the method has the advantages of high specific surface area, large pore volume and low content of impurity sodium, and is a high-quality raw material of high-performance catalysts, adsorbents and high-temperature-resistant ceramic materials.
3. The alumina material prepared by the invention, Al thereof2O3The purity is over 99.96 percent, and the sodium content is lower than 250 ppm; even below 200 ppm; the specific surface area is 140-2The/g is adjustable; the pore volume is 0.68-1.18cm3The/g is adjustable; the basic grains of the alumina crystal are in a shape of a nearly regular hexagon, and the maximum grain diameter is less than 7nm, even less than 6 nm. The alumina has an XRD 2 theta of 48.8 DEG diffraction peak intensity in excess of 600cps, and even as high as 2500 cps.
4. The alumina material with high specific surface area, high pore volume and low sodium content prepared by the invention can be used as automobile exhaust treatment catalyst, catalytic cracking catalyst additive, heavy oil deep hydrogenation impurity removal element (HDS and HDN), fine chemical hydrogenation catalyst carrier, polishing material prepared by electronic products, sewage treatment adsorbent, filtering membrane and raw material for manufacturing precise ceramics.
Drawings
FIG. 1 is a graph comparing the inventive process with a prior art method of analyzing the alumina product produced.
FIG. 2 is an XRD spectrum of the alumina material prepared in examples 1 to 4 of the present invention.
Fig. 3 is a graph showing the correlation between the XRD diffraction peak 2 θ of 48.8 ° and the specific surface area of the alumina material prepared in examples 1 to 4 of the present invention.
Fig. 4 is a Scanning Electron Microscope (SEM) photomicrograph of the alumina material prepared in example 1 of the present invention.
Fig. 5 is a graph showing the results of Scanning Transmission Electron Microscope (STEM) lattice imaging of the alumina material prepared in example 1 of the present invention.
Fig. 6 is a graph showing the results of Scanning Transmission Electron Microscope (STEM) lattice imaging of the alumina material prepared in example 3 of the present invention.
FIG. 7 is a graph showing the results of laser particle size analysis of alumina particles formed during the reaction of sodium metaaluminate with carbon dioxide in the preparation process of example 1 of the present invention.
FIG. 8 is a graph showing the amount of alumina formed during the reaction of sodium metaaluminate with carbon dioxide in the production process of example 1 of the present invention as a function of reaction time.
FIG. 9 shows the results of laser particle size analysis of the aged product of alumina produced during the reaction of sodium metaaluminate with carbon dioxide in the preparation process of example 1 of the present invention.
Detailed Description
The invention is further illustrated below with reference to the figures and examples.
Comparative example
Alumina powder of high specific surface area and high pore volume was purchased from Shandong aluminum Zibo as control sample A. The specific surface area and the sodium content are shown in Table 1. This sample A had a very high specific surface area of 325.1m2(ii)/g; the pore volume is up to 1.45cm3(ii)/g; the aperture is 18 nm; the sodium content was 410 ppm; its isoelectric point was 8.7.
Composition and structural analysis results of alumina samples prepared in Table 1, comparative example, examples 1 to 4
Figure BDA0002963023220000051
Figure BDA0002963023220000061
Example 1
A method for rapidly preparing a high-performance aluminum oxide material comprises the following steps:
(1) preparing a sodium metaaluminate solution: 795.06g of deionized water is weighed and put into a stainless steel container with a volume of 2 liters and a polytetrafluoroethylene lining, stirring is started (120RPM), sodium hydroxide (Tianjin chemical reagent, the water content is lower than 1.7 percent) of analytical purity is added, the adding speed is proper to prevent bottom caking, and 203.31g of sodium hydroxide is added in total; heating the system to ensure that the temperature of the system reaches 82 ℃; the starting material, aluminium hydroxide (ATH), having a free water content of 2.7%, 418.57g, was added gradually to the above sodium hydroxide solution, and after the addition of ATH was complete, the vessel was capped and stirring was continued, keeping the temperature of the system at 93 ℃ until a nearly transparent liquid was obtained (without ATH particles).
(2) Removing impurities: cooling the liquid obtained in the step (1) to 47 ℃, stopping stirring, standing for 15.5 minutes, removing solid matters deposited below the container, and obtaining clear liquid as a raw material for synthesizing the alumina;
(3) preparing aluminum oxide: diluting the clear liquid obtained in the step (2), wherein the concentration of the diluted clear liquid is 45% of that before dilution; reacting the diluted clear liquid with mixed gas containing carbon dioxide to obtain alumina crystals, which comprises the following steps: transferring the diluted clear liquid into an open reactor with a gas distribution disc at the bottom, wherein the diameter of the reactor is 8cm, and the height of the reactor is 35 cm; then introducing mixed gas containing carbon dioxide from the bottom of the reactor, uniformly dispersing the gas entering from the bottom into bubbles by using a gas distribution disc, carrying out full gas-liquid reaction with liquid, reacting the carbon dioxide with sodium hydroxide to form sodium carbonate and sodium bicarbonate, and discharging reaction tail gas from the upper part of the reactor; the flow rates of carbon dioxide and air (gas cylinder-shaped zero air) are controlled by a rotor flow meter; the reactor is provided with an internal coil pipe to heat or extract heat from materials in the container; introducing ice water into the coil pipe, and controlling the temperature of the reaction system by controlling the flow of the cold water, wherein the temperature control system is realized by adopting an Omega CN76000 PID temperature controller; controlling the content of carbon dioxide in the carbon dioxide mixed gas to be 35.3 vol.%; the air inlet speed was 17.4L/L diluted supernatant/min. The reaction temperature is controlled between 23.7 ℃ and 24.3 ℃; the total reaction time was 14 minutes; the reaction product is a white precipitate;
(4) aging of reaction products: transferring the solid-liquid mixture reacted in the step (3) into a container with a stirring and temperature control system for aging, controlling the aging temperature at 72.5 ℃, controlling the stirring speed at the linear velocity of the tail end of a stirring paddle at 0.98m/s, and aging for 1.6 hours;
(5) taking 100 ml of the solid-liquid mixture in the step (4), and carrying out centrifugal separation and washing on the solid-liquid mixture. Centrifuging with U.S. Thermo Multifuge-1L, using polymer centrifugation container supplied by manufacturer, each 50 ml volume; the centrifuge speed was 1250RPM with a centrifuge vessel end line speed of 26.2 m/s. The weight ratio of wash liquor to solid was 6.5:1, washing was carried out until the conductivity of the wash liquor was 50. mu.S/c or below. Marking the centrifuged solid sample as B, and performing X-ray diffraction (XRD) analysis; the scanning speed is 0.001 degree/s; the 2 theta scanning range is 5-75 degrees; a copper target X-ray source is adopted, and a Bruker D8 diffractometer is adopted; a LynxEye detector is adopted; the qualitative identification of the formation structure of alumina and the quantitative determination of the alumina production were carried out by using a diffraction peak of 48.8 ° 2 θ. DIFFRACC (digital image and data interchange) analysis software carried by Bruker instrumentPlusBASIC performs qualitative and quantitative analyses. The synthesis process of the aluminum oxide is controlled and optimized by the XRD segregation reducing result.
The XRD pattern of the alumina sample B is shown as curve B in FIG. 2, and the correlation between the XRD diffraction peak 2 theta (48.8 degrees) and the specific surface area of the alumina product prepared in examples 1-4 is shown as curve B in FIG. 3. Wherein the point B is a correlation diagram of the XRD diffraction peak 2 theta of the sample B which is 48.8 DEG peak height and the specific surface area thereof.
FIG. 4 is a Scanning Electron Microscope (SEM) micrograph of alumina sample B showing that this sample consists essentially of 2-10 microns of agglomerated crystals.
FIG. 5 shows the Scanning Transmission Electron Microscope (STEM) lattice imaging result of the alumina sample B, in which the lattice and size of the single crystal grain can be clearly seen, which shows that the morphology of the single crystal grain of the product is 4-5nm, and the single crystal grain is a highly symmetrical near-hexagonal body.
(6) And (4) carrying out degassing treatment and roasting treatment on the sample B obtained in the step (5) to obtain a sample, and carrying out specific surface area (BET) analysis, pore volume analysis and pore size analysis on the sample. Degassing was carried out using VacPrep061 from Micromeritics, USA, at a final degassing temperature of 350 ℃ for 120 minutes. Degassing was carried out in a Micromeritics TriStar specific sample tube. The treated sample can be directly put into TriStar for surface area, pore volume and pore diameter analysis. And (4) carrying out data processing and analysis by adopting self-contained software of the instrument. The measurement results are shown in Table 1.
(7) And (4) digesting and oxygen-generating the sample B obtained in the step (5) to analyze the sodium content of the sample B. The precision can reach 0.5ppm by adopting an ULA-100 flame spectrophotometer produced by Beijing Jingke instruments company for micro-quantification. The measurement results are shown in Table 1.
(8) And (4) carrying out surface potential measurement on the sample B obtained in the step (5). The measurement was carried out using ZetaPals produced by Brookhaven instruments of America. The instrument is calibrated by adopting a Ludox-DW40 nanometer silica gel sample to ensure the reliability of the instrument. The preparation of the sample to be analyzed was carried out using a 1mM potassium chloride solution. The pH adjustment of the sample was carried out using a 1.0M sodium hydroxide solution or a 1.0M nitric acid solution. The measurement results are shown in Table 1.
(9) Product separation: and (4) filtering the solid-liquid mixture in the step (4) while the solid-liquid mixture is hot. Filtration was carried out using a 2 liter suction filtration funnel (Jiangsu Kuer Fine ceramics technology Co., Ltd.) using Whatman chemical-resistant filter paper in USA. The filter cake was washed with secondary reverse osmosis deionized water (Tongtai water treatment facility, Inc., Qingzhou, Shandong). And (5) obtaining the final aluminum oxide material product when the conductivity of the washing liquid is less than 50 mu S/cm.
Example 2
A method for rapidly preparing a high-performance aluminum oxide material comprises the following steps:
(1) preparing a sodium metaaluminate solution: weighing 821.94g of deionized water, placing into a stainless steel container with a volume of 2L and a polytetrafluoroethylene lining, starting stirring (95RPM), adding analytically pure sodium hydroxide (Tianjin chemical reagent, the water content is lower than 1.7%), and adding 220.73g of sodium hydroxide at a proper speed without bottom caking; heating the system to enable the temperature of the system to reach 79 ℃; the starting material, aluminium hydroxide (ATH), with a free water content of 2.7%, 430.19g, was added gradually to the above sodium hydroxide solution, and after the addition of ATH was complete, the vessel was capped and stirring was continued, keeping the temperature of the system at 95 ℃ until a nearly transparent liquid was obtained (without ATH particles).
(2) Removing impurities: cooling the liquid obtained in the step (1) to 53 ℃, stopping stirring, standing for 12.3 minutes, and removing solid matters deposited at the bottom of the container to obtain clear liquid serving as a raw material for synthesizing the alumina;
(3) preparing aluminum oxide: diluting the clear liquid obtained in the step (2), wherein the concentration of the diluted clear liquid is 45% of that before dilution; reacting the diluted clear liquid with gas containing carbon dioxide to obtain alumina crystals, which comprises the following steps: transferring the diluted clear liquid into an open reactor with a gas distribution disc at the bottom, wherein the diameter of the reactor is 8cm, and the height of the reactor is 35 cm; then introducing mixed gas containing carbon dioxide from the bottom of the reactor, uniformly dispersing the gas entering from the bottom into bubbles by using a gas distribution disc, carrying out full gas-liquid reaction with liquid, reacting the carbon dioxide with sodium hydroxide to form sodium carbonate and sodium bicarbonate, and discharging reaction tail gas from the upper part of the reactor; the flow rates of carbon dioxide and air (gas cylinder-shaped zero air) are controlled by a rotor flow meter; the reactor is provided with an internal coil pipe to heat or extract heat from materials in the container; introducing ice water into the coil pipe, and controlling the temperature of the reaction system by controlling the flow of the cold water, wherein the temperature control system is realized by adopting an Omega CN76000 PID temperature controller; controlling the content of carbon dioxide in the carbon dioxide mixed gas to be 51.2 vol%; the air inlet speed was 20.7L/L diluted supernatant/min. The reaction temperature is controlled between 25.6 ℃ and 26.2 ℃; the total reaction time was 8 minutes; the reaction product is a white precipitate;
(4) aging of reaction products: transferring the solid-liquid mixture obtained in the step (3) into a container with a stirring and temperature control system for aging, controlling the aging temperature at 82.6 ℃, controlling the stirring speed at the linear velocity of the tail end of a stirring paddle at 1.65m/s, and aging for 3.2 hours;
(5) taking 100 ml of the solid-liquid mixture in the step (4), and carrying out centrifugal separation and washing on the solid-liquid mixture. Centrifuging with U.S. Thermo Multifuge-1L, using polymer centrifugation container supplied by manufacturer, each 50 ml volume; the centrifugation speed was 1050RPM, and the linear velocity at the end of the centrifugation vessel was 22.0 m/s. The weight ratio of the washing liquid to the solid was 7.3:1, and the supernatant was washed until the conductivity of the supernatant was 47. mu.S/cm. Marking the centrifuged solid sampleRecord as sample C, perform X-ray diffraction (XRD) analysis; the scanning speed is 0.001 degree/s; the 2 theta scanning range is 5-75 degrees; a copper target X-ray source is adopted, and a Bruker D8 diffractometer is adopted; a LynxEye detector is adopted; the qualitative identification of the formation structure of alumina and the quantitative determination of the alumina production were carried out by using a diffraction peak of 48.8 ° 2 θ. DIFFRACC (digital image and data interchange) analysis software carried by Bruker instrumentPlusBASIC performs qualitative and quantitative analyses. The XRD analysis result is used for controlling and optimizing the synthesis process of the alumina.
The curve C in fig. 2 is the XRD spectrum of the alumina sample C, and the point C in fig. 3 is the correlation between the XRD diffraction peak 2 θ of the alumina sample C, which is 48.8 ° peak height, and the specific surface area thereof.
(6) And (4) carrying out degassing treatment and roasting treatment on the sample C obtained in the step (5) to obtain a sample, and carrying out specific surface area (BET), pore volume and pore diameter analysis on the sample. Degassing was carried out using VacPrep061 from Micromeritics, USA, at a final degassing temperature of 350 ℃ for 120 minutes. Degassing was carried out in a Micromeritics TriStar specific sample tube. The treated sample can be directly put into TriStar for surface area, pore volume and pore diameter analysis. And (4) carrying out data processing and analysis by adopting self-contained software of the instrument. The measurement results are shown in Table 1.
(7) And (4) digesting and oxygen-generating the sample C obtained in the step (5) to analyze the sodium content of the sample C. The precision can reach 0.5ppm by adopting an ULA-100 flame spectrophotometer produced by Beijing Jingke instruments company for micro-quantification. The measurement results are shown in Table 1.
(8) And (4) carrying out surface potential measurement on the sample C obtained in the step (5). The measurement was carried out using ZetaPals produced by Brookhaven instruments of America. The instrument is calibrated by adopting a Ludox-DW40 nanometer silica gel sample to ensure the reliability of the instrument. The preparation of the sample to be analyzed was carried out using a 1mM potassium chloride solution. The pH adjustment of the sample was carried out using a 1.0M sodium hydroxide solution or a 1.0M nitric acid solution. The measurement results are shown in Table 1.
(9) Product separation: and (4) filtering the solid-liquid mixture in the step (4) while the solid-liquid mixture is hot. Filtration was carried out using a 2 liter suction filtration funnel (Jiangsu Kuer Fine ceramics technology Co., Ltd.) using Whatman chemical-resistant filter paper in USA. The filter cake was washed with secondary reverse osmosis deionized water (Tongtai water treatment facility, Inc., Qingzhou, Shandong). The conductivity of the washing liquid is less than 50 mu S/cm.
Example 3
A method for rapidly preparing a high-performance aluminum oxide material comprises the following steps:
(1) preparing a sodium metaaluminate solution: weighing 934.82g of deionized water, placing into a stainless steel container with a volume of 2L and a polytetrafluoroethylene lining, starting stirring (162RPM), adding analytically pure sodium hydroxide (Tianjin chemical reagent, the water content is lower than 1.7%), and adding 162.86g of sodium hydroxide at a proper speed without bottom caking; heating the system to enable the temperature of the system to reach 73 ℃; the starting material, aluminium hydroxide (ATH), with a free water content of 2.7%, 377.59g, was added gradually to the above sodium hydroxide solution, and after the addition of ATH was complete, the vessel was capped and stirring was continued, keeping the temperature of the system at 91 ℃ until a nearly transparent liquid was obtained (without ATH particles).
(2) Removing impurities: cooling the liquid obtained in the step (1) to 48 ℃, stopping stirring, standing for 10.2 minutes, and removing solid matters deposited below the container to obtain clear liquid serving as a raw material for synthesizing the aluminum oxide;
(3) preparing aluminum oxide: diluting the clear liquid obtained in the step (2), wherein the concentration of the diluted clear liquid is 46.2% of that before dilution; reacting the diluted clear liquid with gas containing carbon dioxide to obtain alumina crystals, which comprises the following steps: transferring the diluted clear liquid into an open reactor with a gas distribution disc at the bottom, wherein the diameter of the reactor is 8cm, and the height of the reactor is 35 cm; then introducing mixed gas containing carbon dioxide from the bottom of the reactor, uniformly dispersing the gas entering from the bottom into bubbles by using a gas distribution disc, carrying out full gas-liquid reaction with liquid, reacting the carbon dioxide with sodium hydroxide to form sodium carbonate and sodium bicarbonate, and discharging reaction tail gas from the upper part of the reactor; the flow rates of carbon dioxide and air (gas cylinder-shaped zero air) are controlled by a rotor flow meter; the reactor is provided with an internal coil pipe to heat or extract heat from materials in the container; introducing ice water into the coil pipe, and controlling the temperature of the reaction system by controlling the flow of the cold water, wherein the temperature control system is realized by adopting an Omega CN76000 PID temperature controller; controlling the content of carbon dioxide in the carbon dioxide mixed gas to be 26.7 vol.%; the air inlet speed was 17.4L/L diluted supernatant/min. The reaction temperature is controlled between 25.6 ℃ and 26.2 ℃; the total reaction time was 12 minutes; the reaction product is a white precipitate;
(4) aging of reaction products: transferring the solid-liquid mixture obtained in the step (3) into a container with a stirring and temperature control system for aging, controlling the aging temperature at 68.5 ℃, controlling the stirring speed at the linear velocity of the tail end of a stirring paddle at 2.0m/s, and aging for 0.8 hour;
(5) taking 100 ml of the solid-liquid mixture in the step (4), and carrying out centrifugal separation and washing on the solid-liquid mixture. Centrifuging with U.S. Thermo Multifuge-1L, using polymer centrifugation container supplied by manufacturer, each 50 ml volume; the centrifugation speed was 1500RPM and the linear velocity at the end of the centrifuge vessel was 31.4 m/s. The weight ratio of the washing liquid to the solid was 5.3:1, and the supernatant was washed until the conductivity of the supernatant was 42. mu.S/cm. Marking the centrifuged solid sample as a sample D, and carrying out X-ray diffraction (XRD) analysis; the scanning speed is 0.001 degree/s; the 2 theta scanning range is 5-75 degrees; a copper target X-ray source is adopted, and a Bruker D8 diffractometer is adopted; a LynxEye detector is adopted; the qualitative identification of the formation structure of alumina and the quantitative determination of the alumina production were carried out by using a diffraction peak of 48.8 ° 2 θ. DIFFRACC (digital image and data interchange) analysis software carried by Bruker instrumentPlusBASIC performs qualitative and quantitative analyses. The XRD analysis result is used for controlling and optimizing the synthesis process of the alumina.
The curve D in fig. 2 is the XRD spectrum of the alumina sample D, and the point D in fig. 3 is the correlation between the XRD diffraction peak 2 θ of the alumina sample D, which is 48.8 ° peak height, and the specific surface area thereof.
Fig. 6 is a graph of the results of Scanning Transmission Electron Microscope (STEM) lattice imaging of alumina sample D. It is clearly seen that the lattice size of the individual grains is 4-5nm, as: the white dotted circle in the figure shows a typical regular hexagonal morphology.
(6) And (4) carrying out degassing treatment and roasting treatment on the sample D obtained in the step (5) to obtain a sample, and carrying out specific surface area (BET), pore volume and pore diameter analysis on the sample. Degassing was carried out using VacPrep061 from Micromeritics, USA, at a final degassing temperature of 350 ℃ for 120 minutes. Degassing was carried out in a Micromeritics TriStar specific sample tube. The treated sample can be directly put into TriStar for surface area, pore volume and pore diameter analysis. And (4) carrying out data processing and analysis by adopting self-contained software of the instrument. The measurement results are shown in Table 1.
(7) And (5) digesting and oxygen-generating the sample D obtained in the step (5) to analyze the sodium content of the sample D. The precision can reach 0.5ppm by adopting an ULA-100 flame spectrophotometer produced by Beijing Jingke instruments company for micro-quantification. The measurement results are shown in Table 1.
(8) And (4) carrying out surface potential measurement on the sample D obtained in the step (5). The measurement was carried out using ZetaPals produced by Brookhaven instruments of America. The instrument is calibrated by adopting a Ludox-DW40 nanometer silica gel sample to ensure the reliability of the instrument. The preparation of the sample to be analyzed was carried out using a 1mM potassium chloride solution. The pH adjustment of the sample was carried out using a 1.0M sodium hydroxide solution or a 1.0M nitric acid solution. The measurement results are shown in Table 1.
(9) Product separation: and (4) filtering the solid-liquid mixture in the step (4) while the solid-liquid mixture is hot. Filtration was carried out using a 2 liter suction filtration funnel (Jiangsu Kuer Fine ceramics technology Co., Ltd.) using Whatman chemical-resistant filter paper in USA. The filter cake was washed with secondary reverse osmosis deionized water (Tongtai water treatment facility, Inc., Qingzhou, Shandong). The conductivity of the washing liquid is less than 50 mu S/cm.
Example 4
A method for rapidly preparing a high-performance aluminum oxide material comprises the following steps:
(1) preparing a sodium metaaluminate solution: weighing 1921.27g of deionized water, putting the deionized water into a stainless steel container (Pressure Product Industry Inc. PPI-AC8, USA, the polytetrafluoroethylene lining is filled inside) with the volume of 4 liters, starting stirring (230RPM), adding analytically pure sodium hydroxide (Tianjin chemical reagent, the moisture content is lower than 1.7 percent), and adding 559.43g of sodium hydroxide in total at a speed which is suitable for avoiding bottom caking; starting a feeding sleeve for heating to heat the system, so that the temperature of the system reaches 65 ℃; the starting material, aluminium hydroxide (ATH), with a free water content of 2.7%, 1147.52g, was added gradually to the above sodium hydroxide solution, and after the addition of ATH was complete, the vessel was capped and stirring was continued, keeping the temperature of the system at 93 ℃ until a nearly transparent liquid was obtained (without ATH particles).
(2) Removing impurities: cooling the liquid obtained in the step (1) to 43 ℃, stopping stirring, standing for 17 minutes, and removing solid matters deposited at the bottom of the container to obtain clear liquid serving as a raw material for synthesizing the alumina;
(3) preparing aluminum oxide: diluting the clear liquid obtained in the step (2), wherein the concentration of the diluted clear liquid is 46.2% of that before dilution; reacting the diluted clear liquid with gas containing carbon dioxide to obtain the alumina HPVA, which comprises the following specific steps: transferring the diluted clear liquid into an open reactor with a gas distribution disc at the bottom, wherein the diameter of the reactor is 8cm, and the height of the reactor is 35 cm; then introducing mixed gas containing carbon dioxide from the bottom of the reactor, uniformly dispersing the gas entering from the bottom into bubbles by using a gas distribution disc, carrying out full gas-liquid reaction with liquid, reacting the carbon dioxide with sodium hydroxide to form sodium carbonate and sodium bicarbonate, and discharging reaction tail gas from the upper part of the reactor; the flow rates of carbon dioxide and air (gas cylinder-shaped zero air) are controlled by a rotor flow meter; the reactor is provided with an internal coil pipe to heat or extract heat from materials in the container; introducing ice water into the coil pipe, and controlling the temperature of the reaction system by controlling the flow of the cold water, wherein the temperature control system is realized by adopting an Omega CN76000 PID temperature controller; controlling the content of carbon dioxide in the carbon dioxide mixed gas to be 33.4 vol.%; the air inlet speed is 20.9L/L diluted clear liquid/min. The reaction temperature is controlled between 23.3 ℃ and 24.2 ℃; the total reaction time was 12 minutes; the reaction product is a white precipitate;
(4) aging of reaction products: transferring the solid-liquid mixture obtained in the step (3) into a container with a stirring and temperature control system for aging, controlling the aging temperature at 78.4 ℃, controlling the stirring speed at the linear velocity of the tail end of a stirring paddle at 1.2m/s, and aging for 2.4 hours;
(5) taking 100 ml of the solid-liquid mixture in the step (4), and carrying out centrifugal separation and washing on the solid-liquid mixture. Centrifuging with U.S. Thermo Multifuge-1L, using polymer centrifugation container supplied by manufacturer, each 50 ml volume; the centrifugal speed is 1500RPM, its centrifugal container end linear velocity is 31.4 m/s. The weight ratio of the washing liquid to the solid was 5.3:1, and the supernatant was washed until the conductivity of the supernatant was 42. mu.S/cm. Marking the centrifuged solid sample as sample E, and carrying out X-ray diffraction (XRD) analysis; the scanning speed is 0.001 degree/s; the 2 theta scanning range is 5-75 degrees; a copper target X-ray source is adopted, and a Bruker D8 diffractometer is adopted; a LynxEye detector is adopted; the qualitative identification of the formation structure of alumina and the quantitative determination of the alumina production were carried out by using a diffraction peak of 48.8 ° 2 θ. DIFFRACC (digital image and data interchange) analysis software carried by Bruker instrumentPlusBASIC performs qualitative and quantitative analyses. The XRD analysis result is used for controlling and optimizing the synthesis process of the alumina.
The curve E in fig. 2 is the XRD spectrum of the alumina sample E, and the point E in fig. 3 is the correlation between the XRD diffraction peak 2 θ of the alumina sample E, which is 48.8 ° peak height, and the specific surface area thereof.
(6) And (4) carrying out degassing treatment and roasting treatment on the sample E obtained in the step (5) to obtain a sample, and carrying out specific surface area (BET), pore volume and pore diameter analysis on the sample. Degassing was carried out using VacPrep061 from Micromeritics, USA, at a final degassing temperature of 350 ℃ for 120 minutes. Degassing was carried out in a Micromeritics TriStar specific sample tube. The treated sample can be directly put into TriStar for surface area, pore volume and pore diameter analysis. And (4) carrying out data processing and analysis by adopting self-contained software of the instrument. The measurement results are shown in Table 1.
(7) And (5) digesting and oxygen-generating the sample E obtained in the step (5) to analyze the sodium content of the sample E. The precision can reach 0.5ppm by adopting an ULA-100 flame spectrophotometer produced by Beijing Jingke instruments company for micro-quantification. The measurement results are shown in Table 1.
(8) And (4) carrying out surface potential measurement on the sample E obtained in the step (5). The measurement was carried out using ZetaPals produced by Brookhaven instruments of America. The instrument is calibrated by adopting a Ludox-DW40 nanometer silica gel sample to ensure the reliability of the instrument. The preparation of the sample to be analyzed was carried out using a 1mM potassium chloride solution. The pH adjustment of the sample was carried out using a 1.0M sodium hydroxide solution or a 1.0M nitric acid solution. The measurement results are shown in Table 1.
(9) Product separation: and (4) filtering the solid-liquid mixture in the step (4) while the solid-liquid mixture is hot. Filtration was carried out using a 5-liter suction filtration funnel (Jiangsu Kuer Fine ceramics technology Co., Ltd.) using Whatman chemical-resistant filter paper in USA. The filter cake was washed with secondary reverse osmosis deionized water (Tongtai water treatment facility, Inc., Qingzhou, Shandong). The conductivity of the washing liquid is less than 50 mu S/cm.
As a further examination of the conditions for the preparation of alumina, the reaction of sodium metaaluminate solution with carbon dioxide to produce alumina product and the optimization of the aging process, the particle size analysis of the alumina sample in step (3) of example 1 was carried out, and the results are shown in FIG. 7. It can be seen that large particles have formed, the average particle size d of which5010.2 nm.
By measuring the formation of precipitates at different reaction stages, the reaction time can be accurately controlled as shown in FIG. 8, which shows that the carbonization reaction has been completed after 12 minutes of reaction. The particle size analysis of the aged sample of step (4) was carried out, and the results are shown in FIG. 9. We have found that aging can further adjust the size of the agglomerated alumina particles. Aging is effective to reduce the average size of the alumina particles. FIG. 9 shows the particle size from d after 15 min of aging50Decrease to d at 10.2 μm50＝7.0μm。
The above examples demonstrate that by controlling the alumina concentration, sodium hydroxide, carbon dioxide gas concentration and reaction time during synthesis in combination with agitation and gas-liquid reaction mass transfer, controlling the reaction temperature and aging, the present invention achieves low sodium (less than 250ppm, even as low as 3ppm), high specific surface area (up to nearly 300 m)2G), high pore volume (up to approximately 1.5 cm)3A high-quality alumina material of/g).
The analysis and test method adopted in the invention is as follows:
1. the crystal structure of the alumina samples was determined using a powder X-ray instrument Discover D8 from Bruker, germany, with a LynxEye high resolution detector under the following conditions: cu Kalpha target, graphite single crystal device, tube pressure of 40kV, tube flow of 20mA, scanning speed of 12 DEG/min, 2 theta of 5-80 DEG, and test result is processed by Origin software.
2. The morphology of the alumina samples was performed using a scanning electron microscope TM-1000 by Hitachi, japan, the samples were not gold plated, the sample holders were coated with conductive tape, and then different areas were selected for observation and imaging.
3. The high power microscopic imaging analysis of the alumina powder sample adopts a scanning transmission electron microscope Tecnai G2F 30 STEM of the FEI instruments company in America. The powder sample is directly put into a special sample transfer device equipped with an FEI instrument. And adopting a special carbon net for FEI as sample conduction and imaging focusing reference.
4. The specific surface area of the alumina samples was determined using a TriStar specific surface area apparatus, Inc. of instruments, Micromerics. The sample is subjected to degassing pretreatment before measurement, and degassing is carried out by a purging type degassing station of Micromeritics VacPre 061, wherein the degassing process is divided into two stages: namely purging with 30ml/min nitrogen for 30min at room temperature; then, after the temperature was raised to 350 ℃, nitrogen gas of 30ml/min was purged for 2 hours.
5. The granulometry of the alumina samples was analyzed using a MS-2000 laser granulometer from Malvern instruments, UK. The sample is measured by a wet method, namely, a sample to be measured is added into a certain dispersing agent (such as water and water containing the dispersing agent), and a proper refraction factor and shading degree are selected for measurement. Verification was performed before measurement using a Quality Audio Standards 15-150 micron standard Bottle #25782 from Malvern.
6. The isoelectric point (IEP) of the alumina samples was measured using ZetaPals, brueck black text (Brookhaven) instruments, usa, for surface potential measurements. The instrument was calibrated using a Ludox-TM ESA nanosilica standard purchased from Dispersion Technology Inc., USA, at a surface potential of-38 mV at 25 ℃.
7. The formation of solid products during the synthesis of alumina is quantified by means of a high-speed centrifuge. U.S. Thermo Multifuge 1L was used. The liquid sample from the synthesis process was put into 50 ml (4 per centrifuge chamber) sample containers of a high-speed centrifuge for solid-liquid separation. The centrifugal separation rotating speed can reach 3850 revolutions per minute at most. Centrifuge for 2.5 minutes and collect the solid sample at the bottom of the vessel, supernatant. The amount of the separated solid sample (wet basis) was used as a calculation of the solid yield. Dry basis yield further drying and baking of the sample is required to obtain the dry basis yield.
8. And (3) pH measurement: a Thermo Electron Orion 3Star Portable pH meter was used. Before measurement, three-point method is carried out for pH correction.
9. And (3) conductivity measurement: conductance measurements were performed using a Thermo Orion 3Star Portable Conductivity meter. Before the measurement, 1-1000mmol potassium chloride solution is used for calibration.
10. Skeletal density (SKD): the true density, or also called skeleton density, of the material is obtained by helium filling. The true density measurements were carried out using an AccuPyc 1330 Pycnometer from Micromeritics instruments USA, with high purity helium as the measurement medium. The sample size is usually 3-5 g. SKD is in g/mL.

Claims (9)

1. A method for rapidly preparing a high-performance aluminum oxide material is characterized by comprising the following steps:
(1) preparing a sodium metaaluminate solution: adding sodium hydroxide into a container filled with deionized water under the condition of stirring, and controlling the temperature of the system to be 65-82 ℃ to prepare a sodium hydroxide solution; adding aluminum hydroxide into the prepared sodium hydroxide solution, continuously stirring, and controlling the system temperature to be 90-95 ℃ until a nearly transparent liquid, namely a sodium metaaluminate solution, is obtained;
(2) removing impurities: cooling the sodium metaaluminate solution obtained in the step (1) to below 65 ℃, stopping stirring, standing, removing solid matters deposited at the bottom, and taking the obtained clear liquid as a raw material for synthesizing the aluminum oxide material;
(3) preparing aluminum oxide: diluting the clear liquid obtained in the step (2), and reacting the diluted clear liquid with mixed gas containing carbon dioxide to prepare alumina crystals, wherein the method comprises the following specific steps: transferring the diluted clear liquid into an open reactor with a gas distribution disc arranged at the bottom, introducing mixed gas containing carbon dioxide from the bottom of the reactor, obtaining uniform bubbles through the gas distribution disc, reacting the uniform bubbles with the diluted clear liquid, wherein the reaction temperature is 23-26.5 ℃, the reaction product is a white precipitate, and the reaction tail gas is discharged from the upper part of the reactor;
(4) aging of reaction products: transferring the solid-liquid mixture reacted in the step (3) into a container provided with a stirring and temperature control system for aging, wherein the aging temperature is controlled to be 65-85 ℃, the stirring speed is controlled to be 0.98-2.00 m/s at the linear speed of a stirring paddle, and the aging time is 0.8-3.2 hours;
(5) taking 50-100 ml of the mixture obtained in the step (4), carrying out centrifugal separation and washing on the mixture, wherein the centrifugal speed is 22.00-31.4 m/S in terms of linear velocity, washing the centrifugally separated solid by deionized water, and washing until the conductivity of the washing liquid is less than 50 mu S/cm, wherein the weight ratio of the washing liquid to the solid is 5-8: 1; carrying out X-ray diffraction analysis on the washed solid sample; the scanning speed is 0.001 degree/s; the 2 theta scanning range is 5-75 degrees; a copper target is used as an X-ray source, and a Bruker D8 diffractometer is adopted; a LynxEye detector is adopted; the 2 theta-48.8 DEG diffraction peak is used as the analysis for identifying and quantifying the formation of the alumina material and the formation amount thereof and is used as the basis for controlling the process control and optimizing data of the synthesis process of the alumina material;
(6) product separation: and (4) filtering and separating the solid-liquid mixture obtained in the step (4) while the solid-liquid mixture is hot to obtain a solid product, and washing the solid product by using deionized water until the conductivity of the washing liquid is less than 50 mu S/cm to obtain the final aluminum oxide material product.
2. The method for rapidly preparing a high-performance alumina material according to claim 1, wherein: and (2) the stirring speed in the step (1) is 95-230 RPM.
3. The method for rapidly preparing a high-performance alumina material according to claim 1, wherein: the molar ratio of the deionized water to the sodium hydroxide in the step (1) is 7-13: 1, the molar ratio of the sodium hydroxide to the aluminum hydroxide is 0.98-1.35.
4. The method for rapidly preparing a high-performance alumina material according to claim 1, wherein: and (3) standing for 10-17 min in the step (2).
5. The method for rapidly preparing a high-performance alumina material according to claim 1, wherein: the volume percentage of carbon dioxide in the mixed gas containing carbon dioxide in the step (3) is 25-55 vol%.
6. The method for rapidly preparing a high-performance alumina material according to claim 1, wherein: and (4) the air inlet speed in the step (3) is 17.4-20.9L/L diluted clear liquid/min.
7. The method for rapidly preparing a high-performance alumina material according to claim 1, wherein: the ratio of the height to the diameter of the reactor in the step (3) is 1-1.3: 1.
8. The method for rapidly preparing a high-performance alumina material according to claim 1, wherein: and (5) washing until the conductivity of the washing liquid is less than 15 mu S/cm.
9. The high performance alumina material prepared by the method of any one of claims 1 to 8, wherein: the single crystal morphology of the aluminum oxide material is approximately hexagonal; the purity of the aluminum oxide material is more than 99.96%, the sodium content is less than 250ppm, and the specific surface area is 140-289m2A pore volume of 0.68-1.18 cm/g3/g。
CN202110243082.2A 2021-03-05 2021-03-05 High-performance aluminum oxide material and preparation method thereof Active CN112978773B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110243082.2A CN112978773B (en) 2021-03-05 2021-03-05 High-performance aluminum oxide material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110243082.2A CN112978773B (en) 2021-03-05 2021-03-05 High-performance aluminum oxide material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112978773A true CN112978773A (en) 2021-06-18
CN112978773B CN112978773B (en) 2023-04-18

Family

ID=76352933

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110243082.2A Active CN112978773B (en) 2021-03-05 2021-03-05 High-performance aluminum oxide material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112978773B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10231119A (en) * 1997-02-21 1998-09-02 Mizusawa Ind Chem Ltd Alumina or alumina hydrate having ultralow bulk density, high specific surface area and high porosity, and its production and use
CN1752005A (en) * 2005-10-25 2006-03-29 湘潭大学 Preparation method of ultrafine active aluminium oxide
CN105060323A (en) * 2015-07-23 2015-11-18 厦门大学 High pore volume gamma-aluminium oxide and preparation method therefor
CN106315642A (en) * 2015-06-26 2017-01-11 中国石油化工股份有限公司 Preparation method for pseudo-boehmite and preparation method for gamma-alumina

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10231119A (en) * 1997-02-21 1998-09-02 Mizusawa Ind Chem Ltd Alumina or alumina hydrate having ultralow bulk density, high specific surface area and high porosity, and its production and use
CN1752005A (en) * 2005-10-25 2006-03-29 湘潭大学 Preparation method of ultrafine active aluminium oxide
CN106315642A (en) * 2015-06-26 2017-01-11 中国石油化工股份有限公司 Preparation method for pseudo-boehmite and preparation method for gamma-alumina
CN105060323A (en) * 2015-07-23 2015-11-18 厦门大学 High pore volume gamma-aluminium oxide and preparation method therefor

Also Published As

Publication number Publication date
CN112978773B (en) 2023-04-18

Similar Documents

Publication Publication Date Title
US4663137A (en) Process for producing cerium oxide particulates
CN105032478B (en) A kind of catalyst and its dedicated core-shell structure compound molecular sieve for the oily isomerization-visbreaking of F-T synthetic middle distillates point
CN111137905B (en) ZSM-48 molecular sieve and preparation method thereof
CN109775723B (en) Application of pretreated raw material in preparation of SSZ-13 molecular sieve
CN107597130A (en) Different scale high-specific surface area cerium oxide cupric oxide composite mesopore ball and preparation method
CN109928412A (en) A kind of boehmite and preparation method thereof
CN1802211A (en) Ethylene oxide catalyst
CN107381615A (en) A kind of method and its application of Effective Regulation ceria Mesoporous Spheres particle diameter
CN112978773B (en) High-performance aluminum oxide material and preparation method thereof
WO2020106836A2 (en) Silica alumina composition with improved stability and method for making same
CN115286027B (en) Preparation method and application of aluminum hydroxide lithium salt compound
CN111217387A (en) Three-dimensional flower-like hydroxyl zinc fluoride material, preparation method thereof and application thereof in gas-sensitive detection
CN110732341A (en) Isobutane dehydrogenation catalyst with spherical aluminum-containing double mesoporous molecular sieve silica gel composite as carrier and preparation method and application thereof
CN110627100B (en) Two-stage series method for producing micron-sized calcium carbonate by carbonization method with liquid phase as continuous phase
CN112808298B (en) Catalyst containing hierarchical pore Y-type molecular sieve and preparation method thereof
CN114920293A (en) Preparation method of monoclinic scheelite type spherical bismuth vanadate and bismuth vanadate pigment
CN114477209A (en) Silicon-aluminum molecular sieve and preparation method and application thereof
CN114146725B (en) Acidic cobalt-based composite material and preparation method thereof
Vodorezova et al. Silica Monolith Properties Modified by Reaction Mixture Composition and Calcination Process.
CN110357123A (en) A kind of high crystalline multi-stage porous nano X-type molecular sieve and preparation method thereof
CN113318781A (en) Light gasoline cracking propylene yield-increasing catalyst containing spherical chlorite mesoporous composite material and preparation method and application thereof
CN114425294B (en) Supported adsorbent and preparation method and application thereof
CN110732329B (en) Silica sol containing potassium and preparation method thereof, iron-based Fischer-Tropsch synthesis catalyst and preparation method thereof, and Fischer-Tropsch synthesis method
CN116899528A (en) Preparation method and application of novel material ZCGA based on coal gasification waste residue
EP4353683A1 (en) Gis-type zeolite molded body, adsorption device, separation method, and gis-type zeolite

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