CN112010331A - Industrial preparation method and preparation device of magnesium aluminate spinel powder - Google Patents
Industrial preparation method and preparation device of magnesium aluminate spinel powder Download PDFInfo
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- CN112010331A CN112010331A CN202010936348.7A CN202010936348A CN112010331A CN 112010331 A CN112010331 A CN 112010331A CN 202010936348 A CN202010936348 A CN 202010936348A CN 112010331 A CN112010331 A CN 112010331A
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 73
- 239000011029 spinel Substances 0.000 title claims abstract description 73
- 239000000843 powder Substances 0.000 title claims abstract description 70
- 239000011777 magnesium Substances 0.000 title claims abstract description 50
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 50
- -1 magnesium aluminate Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000001914 filtration Methods 0.000 claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002699 waste material Substances 0.000 claims abstract description 30
- 239000012535 impurity Substances 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 2
- 239000000395 magnesium oxide Substances 0.000 claims 1
- 239000008213 purified water Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 23
- 238000002156 mixing Methods 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 5
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 229940091250 magnesium supplement Drugs 0.000 description 36
- 239000000084 colloidal system Substances 0.000 description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 235000010344 sodium nitrate Nutrition 0.000 description 5
- 239000004317 sodium nitrate Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010523 cascade reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005049 combustion synthesis Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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
- C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/162—Magnesium aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D9/00—Nitrates of sodium, potassium or alkali metals in general
-
- 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
- C01P2006/80—Compositional purity
Abstract
The invention provides an industrial preparation method and a preparation device of magnesium aluminate spinel powder, and relates to the technical field of ceramic powder. The industrial preparation method of the magnesia-alumina spinel powder comprises the following steps: mixing magnesium inorganic salt and aluminum inorganic salt according to the mass ratio of Mg ions to Al ions of 1:2 dissolving the mixture in water, dripping alkali liquor for reaction, and adjusting the pH value by using ammonia water to obtain sol; and aging, filtering, removing impurities, drying and dehydrating the sol to obtain a precursor, and finally calcining and grinding the precursor to obtain the high-purity magnesia-alumina spinel powder in a mass production level. The method has the advantages that the sol-gel reaction is complete, no other impurities exist, the mass production can be realized, the prepared magnesia-alumina spinel powder has high purity, the method can be applied to preparation of magnesia-alumina spinel transparent ceramic materials, magnesia-alumina spinel spraying powder and the like, the production cost is greatly reduced, and resources are saved. The preparation device realizes the cyclic utilization of the waste water, reduces the production cost, and reduces or even eliminates the discharge of waste liquid.
Description
Technical Field
The invention relates to the technical field of ceramic powder, in particular to an industrial preparation method and a preparation device of magnesia-alumina spinel powder.
Background
Magnesium aluminate spinel (MgAl)2O4) Spinel (AB) of isometric system2O4) An important structure in a series of compounds. The magnesium aluminate spinel material has the advantages of high temperature resistance, small thermal expansion coefficient, low thermal conductivity, strong corrosion resistance, excellent high-temperature mechanical property and the like. The magnesia-alumina spinel powder can be prepared into conventional transparent ceramic materials and applied to transparent armors, insulating frameworks of electronic components, infrared band window materials and the like. The magnesium aluminate spinel coating can be prepared into spraying powder, and the magnesium aluminate spinel coating can be obtained by plasma spraying and other technologies and can be applied to surface protection of materials with high temperature resistance and corrosion resistance.
The key point of preparing all high-purity magnesium aluminate spinel materials is to obtain high-purity magnesium aluminate spinel powder, and the conventional method for preparing the magnesium aluminate spinel powder comprises three types: solid phase methods, wet chemical methods, and combustion synthesis methods. But they have respective limitations, and although the solid phase method has simple process and low cost, the obtained powder has low purity and large particles; although the wet chemical method has fine and uniform powder particles, the preparation cost is high and the mass production difficulty is large; the combustion synthesis method is efficient and low in cost, but has large and uneven particles.
Therefore, there is a need to develop a process for preparing magnesia-alumina spinel powder with low production cost and high purity of the synthesized magnesia-alumina spinel powder.
Disclosure of Invention
The invention aims to provide an industrial preparation method of magnesia-alumina spinel powder, which can be used for preparing high-purity magnesia-alumina spinel powder and realizing mass production, can be applied to preparing magnesia-alumina spinel transparent ceramic materials, magnesia-alumina spinel spray powder and the like, greatly reduces the production cost and saves resources.
Another object of the present invention is to provide a preparation apparatus suitable for the industrial preparation method of magnesium aluminate spinel powder, which realizes the recycling of waste water, reduces the production cost, and reduces or even eliminates the discharge of waste liquid.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
On the one hand, the application embodiment provides an industrial preparation method of magnesium aluminate spinel powder, which comprises the following steps: the molar quantity ratio of the Mg ions to the Al ions of the magnesium inorganic salt to the aluminum inorganic salt is 1:2 dissolving the mixture in water to prepare a mixed solution; slowly dropping alkali liquor into the mixed solution, adjusting the pH to 11-12 by ammonia water, and stirring for reaction for 0.5-2 h to obtain sol; aging the sol to gelatinize the sol to obtain gel; filtering, removing impurities, drying and dehydrating the gel to obtain a precursor; finally calcining and grinding to obtain the magnesia-alumina spinel powder. The alkaline liquor is slowly dripped and fully stirred, so that the alkaline dripping reaction is more uniform, and the formed colloid is finer.
On the other hand, this application embodiment provides a preparation facilities suitable for aforementioned industrial preparation method of magnesium aluminate spinel powder, including reaction unit, filtration edulcoration device, waste liquid treatment device and the dry calcining device that communicates in proper order, follow the gel that filters the separation of edulcoration device gets into dry calcining device follows the waste liquid of separation gets into waste liquid treatment device in the filtration edulcoration device, waste liquid treatment device's water purification export with reaction unit and/or the water inlet intercommunication of filtering the edulcoration device.
In summary, compared with the prior art, the embodiments of the present invention have at least the following advantages or beneficial effects:
the industrial preparation method of the magnesia-alumina spinel powder solves the problems of uniform mixing, filtration efficiency, thorough impurity removal, complete high-temperature reaction and the like in the mass production powder making process, thereby greatly reducing the production cost and saving resources on the premise of ensuring the product quality. The preparation device provided by the invention realizes the recycling of the waste water, reduces the production cost and reduces or even eliminates the discharge of waste liquid.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an XRD spectrum of a magnesium aluminate spinel obtained by an example of the invention;
FIG. 2 is a schematic view of a manufacturing apparatus provided in the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
On the one hand, the application embodiment provides an industrial preparation method of magnesium aluminate spinel powder, which comprises the following steps: the molar quantity ratio of the Mg ions to the Al ions of the magnesium inorganic salt to the aluminum inorganic salt is 1:2 dissolving the mixture in water to prepare a mixed solution; slowly dropping alkali liquor into the mixed solution, adjusting the pH to 11-12 by ammonia water, and stirring for reaction for 0.5-2 h to obtain sol; aging the sol to gelatinize the sol to obtain gel; filtering, removing impurities, drying and dehydrating the gel to obtain a precursor; finally calcining and grinding to obtain the magnesia-alumina spinel powder. The alkaline liquor is slowly dripped and fully stirred, so that the alkaline dripping reaction is more uniform, and the formed colloid is finer.
In some embodiments of the present invention, the aging time in the industrial preparation method of magnesium aluminate spinel powder is greater than or equal to 12 hours.
In some embodiments of the present invention, the purity of the magnesium aluminate spinel powder in the above-mentioned industrial preparation method of the magnesium aluminate spinel powder is greater than or equal to 99%.
In some embodiments of the present invention, in the above-mentioned industrial preparation method of magnesium aluminate spinel powder, the temperature of water used for dissolving the magnesium inorganic salt and the aluminum inorganic salt and forming the mixed solution is 40 ℃ to 60 ℃, the stirring speed during the preparation of the mixed solution is 100-.
In some embodiments of the present invention, the alkali solution used in the above-mentioned industrial preparation method of magnesium aluminate spinel powder is 15-30mol/L NaOH solution, and the molar quantity ratio of Mg ions in magnesium inorganic salt to OH ions in alkali solution is 1: 8.
In some embodiments of the present invention, the gel obtained in the above-mentioned industrial preparation method of magnesium aluminate spinel powder is filtered, and the method comprises the following steps: filtering the gel through a 10-micron filter bag at a filtering flow rate of 10-20L/h, and filtering the gel through a 3-micron filter bag at a filtering flow rate of 5-10L/h.
In some embodiments of the present invention, the above method for industrially preparing magnesium aluminate spinel powder comprises the following steps: putting the filtered gel into a filter bag with the diameter of 3 mu m, introducing running water into the filter bag, wherein the speed of the water flowing into and out of the filter bag is 2-4L/h, and washing for 4-8 hours by the running water; an ultrasonic emitter is placed in the filter bag in the impurity removal process. Because the gel can absorb various ions in the solution, the purity of the gel is reduced, and the ultrasonic emitter can effectively prevent the gel from absorbing the ions and remove the absorbed ions, thereby improving the purity of the gel.
In some embodiments of the present invention, the gel obtained in the above-mentioned industrial preparation method of magnesium aluminate spinel powder is filtered, and the method comprises the following steps: centrifuging the filtered gel at 2000-4000 r/min for more than or equal to three times, wherein each centrifugation time is 0.5-5 min.
In some embodiments of the present invention, in the above method for industrially preparing magnesium aluminate spinel powder, the gel after impurity removal is dried, and the drying includes the following steps: drying the gel after desalting at 80-100 ℃, and grinding into a precursor with the particle size of less than 100 mu m.
In some embodiments of the present invention, in the above industrial preparation method of magnesium aluminate spinel powder, the precursor is calcined at 1100-1300 ℃ for more than 1h to obtain magnesium aluminate spinel powder.
On the other hand, this application embodiment provides a preparation facilities suitable for aforementioned magnesium aluminate spinel powder's industrial preparation method, including reaction unit, filtration edulcoration device, waste liquid treatment device and the dry calcining device who communicates in proper order, follow the gel of filtration edulcoration device separation gets into dry calcining device follows the waste liquid of separation gets into waste liquid treatment device in the filtration edulcoration device, waste liquid treatment device's water purification export and reaction unit and/or the water inlet intercommunication of filtering the edulcoration device.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The present embodiment aims to provide an industrial preparation method of magnesium aluminate spinel powder, which includes the following steps:
1. mixing materials: adding 20L of water into a 50L reaction kettle, heating the water in the reaction kettle to 40 ℃, pouring 3Kg of magnesium nitrate hexahydrate and 8.8Kg of aluminum nitrate nonahydrate into the water in the reaction kettle, wherein the molar quantity ratio of Mg ions and Al ions is about 1:2, fully dissolving the magnesium nitrate hexahydrate and the aluminum nitrate nonahydrate into the water by stirring with a stirring paddle, and stirring at the rotating speed of 150r/min to obtain a mixed solution.
2. Adding alkali for reaction: weighing about 3.7Kg of NaOH, preparing the NaOH into 20mol/L NaOH solution, cooling the NaOH solution to below 40 ℃, putting the NaOH solution into a titration device of a reaction kettle, gradually dripping the NaOH solution into the mixed solution, controlling the dripping speed to be 80m L/min, finishing dripping within about 1 hour, and controlling the pH value of the sol to be 8-9 after finishing dripping; and then ammonia water is dripped into the sol to adjust the PH value to 11-12, the dripping speed of the ammonia water is 80mL/min, the stirring reaction is continued for 1h after the dripping is finished, and the colloid is obtained after the reaction is finished.
3. And (3) grading and filtering: and (3) filtering the colloid reacted in the step (2) by a 10-micron filter bag at a filtering flow rate of 15L/h, filtering by a 10-micron filter bag and then filtering by a 3-micron filter bag at a filtering flow rate of 8L/h, and repeatedly filtering by water for three times to obtain the filtered colloid.
4. Cleaning and impurity removing: putting the colloid filtered in the step 3 into a filter bag with the diameter of 3 mu m, placing an ultrasonic emitter in the filter bag, arranging flowing water outside the filter bag, wherein the water inlet speed of the flowing water entering the filter bag is 2L/h, the water outlet speed is 2L/h, and after 5 hours of cleaning, the conductivity of the filtrate is close to that of distilled water.
5. And (3) drying: and (4) drying the dialyzed and desalted colloid obtained in the step (4) in a blast oven at the temperature of 80 ℃, and grinding the dried colloid to obtain a ground precursor.
6. And (3) calcining: and (4) calcining the ground precursor obtained in the step (5), controlling the temperature at 1200 ℃, keeping the temperature for 2h, and obtaining the magnesia-alumina spinel powder after calcining, wherein the heating rate is 5 ℃/min and the cooling rate is 5 ℃/min.
7. Grinding: and grinding the calcined magnesia-alumina spinel powder to submicron fine particle powder by a Raymond mill, wherein the yield of the magnesia-alumina spinel is 1.2 Kg.
Example 2
The present embodiment aims to provide an industrial preparation method of magnesium aluminate spinel powder, which includes the following steps:
1. mixing materials: 2 reactors of 50L were connected in series to serve as the reaction vessel of this example, and 25L of water, 50L in total, was added to each of the reactors. And heating the water in the serially connected reaction kettles to 45 ℃, respectively putting reaction substrates into two 50L reaction kettles, wherein the reaction substrates in each reaction kettle comprise 3.5Kg of magnesium nitrate hexahydrate and 10.25Kg of aluminum nitrate nonahydrate, the molar quantity ratio of Mg ions and aluminum ions is about 1:2, fully dissolving the magnesium nitrate hexahydrate and the aluminum nitrate nonahydrate in the water by stirring with a stirring paddle, and stirring at the rotating speed of 200r/min to obtain a mixed solution.
2. Adding alkali for reaction: weighing two parts of NaOH, wherein each part of NaOH is about 4.3Kg, preparing two 20mol/L NaOH solutions, the molar quantity ratio of Mg ions in magnesium inorganic salt to OH ions in alkali liquor is 1:8, cooling to below 40 ℃, respectively placing the two parts of NaOH solutions into a titration device of a reaction kettle, gradually dripping the two parts of NaOH solutions into the mixed solution, controlling the dripping speed of the two parts of NaOH solutions to be 85mL/min, finishing dripping for about 1-2 hours, and controlling the pH of the sol to be 8-9 after finishing dripping; and respectively dripping ammonia water into the sol to adjust the pH value to 11-12, wherein the dripping speed of the ammonia water is 85mL/min, continuously stirring and reacting for 1.5h after dripping is finished, and obtaining the colloid after the reaction is finished.
3. And (3) grading and filtering: and (3) filtering the colloid after the reaction of the reaction kettle connected in series in the step (2) by a 10-micron filter bag at a filtering flow rate of 20L/h, filtering by a 10-micron filter bag and then filtering by a 3-micron filter bag at a filtering flow rate of 10L/h, and repeatedly filtering by water for three times to obtain the filtered colloid.
4. Cleaning and impurity removing: putting the colloid filtered in the step 3 into a filter bag with the diameter of 3 mu m, placing an ultrasonic emitter in the filter bag, arranging flowing water outside the filter bag, wherein the water inlet speed of the flowing water entering the filter bag is 3L/h, the water outlet speed is 3L/h, and after 6 hours of cleaning, the conductivity of the filtrate is close to that of distilled water.
5. And (3) drying: and (4) drying the dialyzed and desalted colloid obtained in the step (4) in a blast oven at the temperature of 90 ℃, and grinding the dried colloid to obtain a ground precursor.
6. And (3) calcining: and (5) calcining the ground precursor obtained in the step (5), controlling the temperature at 1300 ℃, keeping the temperature for 1h, and obtaining the magnesia-alumina spinel powder after calcining, wherein the heating rate is 5 ℃/min and the cooling rate is 5 ℃/min.
7. Grinding: and grinding the calcined magnesia-alumina spinel powder to submicron fine particle powder by a Raymond mill, wherein the yield of the magnesia-alumina spinel is 2.9 Kg.
Example 3
The present embodiment aims to provide an industrial preparation method of magnesium aluminate spinel powder, which includes the following steps:
1. mixing materials: adding 50L of water into a 100L reaction kettle, heating the water in the reaction kettle to 60 ℃, pouring 8Kg of magnesium chloride hexahydrate and 19Kg of aluminum chloride hexahydrate into the water in the reaction kettle, wherein the molar quantity ratio of Mg ions to aluminum ions is about 1:2, and stirring by a stirring paddle to fully dissolve the magnesium nitrate hexahydrate and the aluminum nitrate nonahydrate into the water at the stirring speed of 220r/min to obtain a mixed solution.
2. Adding alkali for reaction: weighing about 12.5Kg of NaOH, preparing the NaOH into 25mol/L NaOH solution, cooling the NaOH solution to below 40 ℃, putting the NaOH solution into a titration device of a reaction kettle, gradually dripping the NaOH solution into the mixed solution, controlling the dripping speed to be 100mL/min, finishing dripping for about 2 hours, and controlling the pH of the sol to be 8-9 after finishing dripping; and then ammonia water is dripped into the sol to adjust the PH value of the sol to 11-12, the dripping speed of the ammonia water is 100mL/min, the mixture is continuously stirred and reacts for 1h after dripping is finished, and colloid is obtained after the reaction is finished.
3. And (3) grading and filtering: and (3) filtering the colloid reacted in the step (2) by a 10-micron filter bag at a filtering flow rate of 20L/h, filtering by a 10-micron filter bag and then filtering by a 3-micron filter bag at a filtering flow rate of 10L/h, and repeatedly filtering by water for three times to obtain the filtered colloid.
4. Cleaning and impurity removing: putting the colloid filtered in the step 3 into a filter bag with the diameter of 3 mu m, placing an ultrasonic emitter in the filter bag, arranging flowing water outside the filter bag, wherein the water inlet speed of the flowing water entering the filter bag is 4L/h, the water outlet speed is 4L/h, and after 7-hour cleaning, the conductivity of the filtrate is close to that of distilled water.
5. And (3) drying: and (4) drying the dialyzed and desalted colloid obtained in the step (4) in a blast oven at the temperature of 80 ℃, and grinding the dried colloid to obtain a ground precursor.
6. And (3) calcining: and (5) calcining the ground precursor obtained in the step (5), controlling the temperature at 1300 ℃, keeping the temperature for 2h, and obtaining the magnesia-alumina spinel powder after calcining, wherein the heating rate is 5 ℃/min and the cooling rate is 5 ℃/min.
7. Grinding: and grinding the calcined magnesia-alumina spinel powder to submicron fine particle powder by a Raymond mill, wherein the yield of the magnesia-alumina spinel is 3.5 Kg.
Example 4
An object of this embodiment is to provide a manufacturing apparatus suitable for the above-mentioned industrial manufacturing method of magnesium aluminate spinel powder, as shown in fig. 2, which specifically includes the following components:
1. reaction device
As shown in fig. 2, the reaction apparatus includes a tandem reaction vessel and an aging apparatus, and the tandem reaction vessel includes a plurality of reaction vessels connected in sequence. The reaction kettle adopts a double-layer design, can add hot circulating water in the middle for temperature control, and is provided with a feed inlet, an alkali liquor titration device, a stirring paddle, a thermocouple and a discharge outlet. After the reaction, the colloid in the reaction kettle can flow into an aging device from a discharge port of the reaction kettle for aging.
The advantages of the reactor series technology are as follows:
the method has the advantages that (1) the investment is not increased basically; (2) mass production is easy to realize on the basis of pilot test; (3) easy to control, for example, when a certain reaction kettle has a problem, other reaction kettles can continue to work; (4) the demand on the reactor itself is reduced.
2. Filtering and impurity removing device
As shown in fig. 2, comprises a grading filter and a colloid impurity removing device. The classifying filter includes two filters, two filter bags and two pumps. The first stage filter is provided with a 10-micron filter bag for filtration; the second stage filter is a 3 micron filter bag. A pump is arranged between the first-stage filter and the second-stage filter, and a pump is also arranged in the second-stage filter and the waste liquid pool, so that the filtering speed of the filter can be accelerated. And introducing the gel from the aging device into a grading filter for repeated filtration for at least 3 times, introducing the gel into an impurity removal device for subsequent reaction, and introducing the waste liquid into a waste liquid treatment system for purification. The colloid impurity removing device comprises an impurity remover, a filter bag and an ultrasonic emitter. The trash remover is provided with a water inlet and a water outlet.
3. Waste liquid treatment device
The waste liquid in the production process (1-3) flows into a waste liquid pool for centralized treatment, the waste liquid may contain nitrate ions, chloride ions and sodium ions, and the PH is always kept in an alkaline state in the reaction process, so that the content of aluminum ions and magnesium ions is extremely low. As shown in fig. 2, the waste liquid treatment is mainly to remove nitrate ions, chloride ions, or sodium ions. Therefore, the system is mainly treated by a physical method, namely, a method of evaporation concentration and solid-liquid separation is adopted for treatment. The first stage evaporated water enters into circulation, and the latter water becomes concentrated waste liquid.
The waste liquid treatment device comprises a primary evaporator and a flash evaporation dryer. The waste liquid passes through a primary evaporator, most of water in the waste liquid can be separated, and the water is collected and can be continuously used in a reaction system, a filtering system and/or an impurity removal system, so that reaction water can be recycled, and concentrated mother liquor can be obtained at the same time. The concentrated sodium nitrate and sodium chloride mother liquor is passed through a flash evaporation dryer to obtain by-products sodium chloride and sodium nitrate, so that the productivity of the whole system is improved.
4. Drying and calcining device
As shown by the expression of (iv) in fig. 2, the drying and calcining apparatus includes a forced air oven, a grinding apparatus, and a high-temperature calciner.
The XRD patterns of the magnesium aluminate spinel obtained in the examples 1-3 are shown in figure 1, wherein the results of the examples 1-3 sequentially correspond to a, b and c in figure 1, and the results show that the method provided by the invention can be used for preparing high-purity magnesium aluminate spinel powder.
It should be noted that the filtration and impurity removal in examples 1 to 3 may be replaced by centrifugation, for example, centrifugation at 2000 to 4000r/min for 0.5 to 5min, and repeated centrifugation for more than three times, and correspondingly, the filtration and impurity removal system in the preparation apparatus may be replaced by a centrifugation system. In addition, NaOH solution can be 15-30mol/L, in the embodiment 1 ~ 3 is the preferred concentration, in addition, can also use other alkali lye.
The industrial preparation method and the preparation device of the magnesia-alumina spinel powder provided by the invention have the advantages that:
(1) in the production process, waste liquid is generated, the waste liquid may contain nitrate ions, chloride ions and sodium ions, and the PH is always kept in an alkaline state in the reaction process, so that the content of aluminum ions and magnesium ions is extremely low. The waste liquid treatment mainly removes nitrate ions, chloride ions and sodium ions. The treatment can be carried out by a physical method, namely, a method of evaporation concentration and solid-liquid separation. The specific operation process comprises the steps of firstly, concentrating the wastewater containing sodium chloride or sodium nitrate in a primary evaporation system, separating most of water in the wastewater, collecting the water, recycling reaction water and simultaneously obtaining concentrated mother liquor, and then further carrying out flash evaporation crystallization and centrifugal separation on the concentrated sodium nitrate and sodium chloride mother liquor to obtain byproducts sodium chloride and sodium nitrate.
(2) The purity of the traditional mass production method cannot reach the purity of a laboratory bench, but the purity of the laboratory bench cannot reach the yield of mass production. The industrial preparation method of the magnesia-alumina spinel powder solves the problems of uniform mixing, filtration efficiency, thorough impurity removal, complete high-temperature reaction and the like in the mass production powder making process, thereby greatly reducing the production cost and saving resources on the premise of ensuring the product quality.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. An industrial preparation method of magnesium aluminate spinel powder is characterized by comprising the following steps: the molar quantity ratio of the Mg ions to the Al ions of the magnesium inorganic salt to the aluminum inorganic salt is 1:2 dissolving the mixture in water to prepare a mixed solution; dripping alkali liquor into the mixed solution, adjusting the pH to 11-12 by ammonia water, and stirring for reaction for 0.5-2 h to obtain sol; aging the sol to gelatinize the sol to obtain gel; filtering, removing impurities, drying and dehydrating the gel to obtain a precursor; finally calcining and grinding to obtain the magnesia-alumina spinel powder.
2. The method of claim 1, wherein the purity of the magnesia alumina spinel powder is greater than or equal to 99%.
3. The industrial preparation method of magnesium aluminate spinel powder according to claim 1, wherein the temperature of water used for dissolving the magnesium inorganic salt and the aluminum inorganic salt and forming the mixed solution is 40 ℃ to 60 ℃, and the rotation speed of stirring when preparing the mixed solution is 100-.
4. The industrial preparation method of magnesium aluminate spinel powder according to claim 1, wherein the alkali solution used in the preparation of the sol is a 15-30mol/L NaOH solution, and the molar quantity ratio of Mg ions in the magnesium inorganic salt to OH ions in the alkali solution is 1: 8.
5. The industrial preparation method of magnesium aluminate spinel powder according to claim 1, wherein the gel obtained is filtered, comprising the steps of: filtering the gel through a 10-micron filter bag at a filtering flow rate of 10-20L/h, and filtering the gel through a 3-micron filter bag at a filtering flow rate of 5-10L/h.
6. The industrial preparation method of magnesium aluminate spinel powder according to claim 5, wherein the step of removing impurities from the filtered gel comprises the following steps: putting the filtered gel into a filter bag with the diameter of 3 mu m, introducing running water into the filter bag, wherein the speed of the water flowing into and out of the filter bag is 2-4L/h, and washing for 4-8 hours by the running water; an ultrasonic emitter is placed in the filter bag in the impurity removal process.
7. The industrial preparation method of magnesium aluminate spinel powder according to claim 1, wherein the gel obtained is filtered, comprising the steps of: centrifuging the filtered gel at 2000-4000 r/min for more than or equal to three times, wherein each centrifugation time is 0.5-5 min.
8. The industrial preparation method of magnesia-alumina spinel powder according to any one of claims 1 to 7, characterized in that the gel after impurity removal is dried, and the drying comprises the following steps: drying the gel after impurity removal at 80-100 ℃, and grinding the gel into a precursor with the particle size of less than 100 mu m.
9. The industrial preparation method of magnesium aluminate spinel powder of claim 8, wherein the precursor is calcined at 1100-1300 ℃ for more than 1h to obtain magnesium aluminate spinel powder.
10. A preparation device suitable for the industrial preparation method of the magnesia-alumina spinel powder as claimed in any one of claims 1 to 9, which comprises a reaction device, a filtration and impurity removal device, a waste liquid treatment device and a drying and calcining device which are sequentially communicated, wherein gel separated from the filtration and impurity removal device enters the drying and calcining device, waste liquid separated from the filtration and impurity removal device enters the waste liquid treatment device, and a purified water outlet of the waste liquid treatment device is communicated with a water inlet of the reaction device and/or the filtration and impurity removal device.
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