CN103332713B - Sandwich type solvent thermal synthesis method of boehmite powder - Google Patents
Sandwich type solvent thermal synthesis method of boehmite powder Download PDFInfo
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Abstract
The invention relates to a sandwich type solvent thermal synthesis method of boehmite powder. The method includes the steps of: dissolving an analytically pure aluminum salt to prepare a transparent solution A with an Al<3+> concentration of 0.1-0.4mol/L, adding a certain amount of a precipitation agent, conducting stirring for half an hour to obtain a transparent solution B, adding a certain amount of phthalate ester into a hydrothermal reaction kettle liner made of polytetrafluoroethylene to form a bottom layer, adding a certain amount of solution B to the upper part of the phthalate ester layer slowly and carefully along the inner wall of the liner to serve as a water layer; adding a certain amount of non-water soluble alcohol to the upper part of the water layer slowly and carefully along the inner wall of the liner so as to form a three-layer sandwich type solvent thermal synthesis system; controlling the solvent thermal temperature at 150-200DEG C, letting the reaction last 12-24h, at the end of the reaction, carrying out natural cooling to room temperature, and finally, opening the hydrothermal reaction kettle, firstly taking out the upper layer alcohol, then employing pumping filtration separation to separate the precipitate from the bottom liquid part, washing the filter cake, then putting it in a vacuum drying box at 80-100DEG C and drying it for 4-8h, thus obtaining the boehmite powder.
Description
Technical field
The present invention relates to a kind of method preparing boehmite superfine powder, the sandwich solvent-thermal method particularly relating to a kind of solvent recoverable prepares the method for different-shape boehmite powder.
Background technology
Boehmite (boehmite) is also known as boehmite, and outward appearance presents white powder, and molecular formula is γ-AlOOH.Boehmite itself can be used as fire retardant and uses, and its most important purposes is prepared alumina powder jointed after being through calcining, therefore is called as the presoma of aluminum oxide.The macroscopic property of the inorganic powder material being representative with boehmite, aluminum oxide, not only depend on its chemical constitution, also be subject to the impact of its size of particles and pattern to a great extent, therefore, the boehmite powder preparing different-shape is the study hotspot in inorganic materials synthesis field all the time.
Take water as medium, prepare in boehmite powder process by hydrothermal method, due to the hydroxyl in water molecules, hydrogen bond is formed with boehmite solid phase surface hydroxyl, the non-bridge formation hydroxyl of adjacent particle can Spontaneous conversion be-O-chemical bond, and the part-structure coordinated water in gel is got rid of, this can cause the close contact between primary particles.In powder drying process subsequently, along with removing further of water, capillary force makes phase interface shrink, and causes growing up of initiating particle, finally forms hard aggregation.
Hard aggregation powder its structure in the application course of processing is not easily destroyed, and will worsen further, causes degradation.The existence of water is the root forming hard aggregation in drying process, and for this reason, people have developed solvent thermal technology, replace water in whole or in part with organic solvent, effectively to eliminate or to reduce the hard aggregation of powder.Because alternative organic solvent is of a great variety, distinct, and the array mode change between different solvents is abundant, therefore organic solvent instead of water is used, not only can reduce the reunion of powder, the synthesis condition of inorganic powder can also be regulated and controled in the larger context, obtain the product of novel pattern.
In prepared by the solvent thermal of boehmite powder, Zhang Liang research group take aluminum chloride as aluminium source, adopts alcohol-water mixing solutions as reaction medium, has successfully prepared one dimension boehmite nanometer rod (the artificial lens journal of big L/D ratio, 2011,40 (4): 892-897); Tang Rui research group with aluminum nitrate and urea for raw material, same employing ethanol-water mixed solvent, prepare foliated lamellar hierarchy construction tufted boehmite presoma, alumina powder jointed (the Chinese Journal of Inorganic Chemistry of identical pattern is obtained after calcining, 2011,27 (2): 251-258); I with Tai-Ace S 150 and urea for raw material, adopt tetrahydrofuran (THF)-water mixed solvent, prepare flower-shaped boehmite powder, obtain after calcining alumina powder jointed (Journal of Shandong agri.Univ (natural science edition) of identical pattern, 2011,42 (4): 511-514).
Alcohol water mixed solvent, the hydroxyl that can replace water with alkoxy portion is formed soft-agglomerated, reduce powder hard aggregation, and tetrahydrofuran (THF)-water mixed solvent, novel floriform appearance boehmite can be prepared, above-mentioned examples prove solvent-thermal method is reducing the validity in powder reuniting and regulation and control morphology microstructure, but does not all mention the recovery of mixed solvent in above-mentioned example.If left, solvent discharge is in environment, both wastes solvent, causes environmental pollution again, too increases cost simultaneously.Considering that solvent is only to provide the environment of reaction, is not reaction raw materials, re-uses after reclaiming, and is completely likely and necessity.But traditional solvent thermal process, reacted solvent presents admixture, is also mingled with water-soluble products, even if after reclaiming, be also difficult to realize abstraction and purification.In addition, conventional solvent thermal means, just with non-aqueous solvent Some substitute water, still there is the existence of water in mixed solvent, the existence of these water, although contribute to the dissolving of aluminium salt, but in powder process of growth, cannot completely isolated water, powder still has an opportunity to touch water molecules, agglomeration can only be alleviate, and but cannot accomplish more thoroughly to eliminate.
Our imagination, can design a kind of solvent and moisture every reaction system, can easily recycling design after reaction terminates, reusable solvent thermal process after simply processing.We utilize density between solvent, boiling point and deliquescent difference, devise a kind of sandwich solvent process for thermosynthesizing, and whole solvent thermal reaction system is divided into bottom, water layer, top layer totally three layers.Bottom is that density is greater than water and the high boiling organic solvent immiscible with water; Water layer has dissolved reaction raw materials, occupy middle; But top layer is then the low boiling point organic solvent that another kind of water insoluble density is less than water.Such as, dimethyl phthalate (relative density 1.191, boiling point 283.7 DEG C, water insoluble, as bottom), be dissolved with aluminum chloride aqueous solution (as water layer) and the n-hexyl alcohol (relative density 0.814 of urea, boiling point 157.0 DEG C, is slightly soluble in water, as top layer) the sandwich solvent thermal reaction system that forms.Although bottom and top layer are all organic solvents, the words encountered one another can occur miscible, because bottom and top layer mass are all water insoluble, and separated by the water layer of centre, so have obvious boundary line between three layers, can not mix between three kinds of solvents, this is also the basis of follow-up solvent recuperation.
The sandwich type structural of such formation, during reacting by heating, because the boiling point of each layer solvent is different, volatilization degree also can be different.Such as, when temperature is 150 DEG C, the dimethyl phthalate (boiling point 283.7 DEG C) of bottom is substantially non-volatile, the water layer of centre is then the most easily vaporized, the urea particularly wherein dissolved, and is namely decomposing generation ammonia and carbonic acid gas more than more than 80 DEG C, the n-hexyl alcohol (boiling point 157.0 DEG C) of top layer, due to temperature of reaction closely its boiling point, also can volatilize in a large number, form the mixing steam of organic solvent and ammoniacal liquor.The boehmite particle formed in solvent thermal reaction process, gathers to a certain degree, will be deposited to the dimethyl phthalate layer of bottom, depart from the impact of water layer completely, contribute to like this improving dispersion of particles by water layer.
After reaction stops and lowering the temperature, due to the difference of solvent density, system has recovered sandwich structure again.For realizing the recycling of solvent, first care should be used to take out whole upper stratas organic solvent and a small amount of water layer with glue head dropper, (there is layering in stratification, represent that upper strata organic solvent layer is all taken out), the organic solvent on upper strata is transferred to the Erlenmeyer flask of band stopper, add siccative (such as anhydrous magnesium sulfate) to dewater, comparatively pure n-hexyl alcohol can be obtained, can reuse.Reaction container bottom is the mixture of boehmite powder, dimethyl phthalate and water layer, first uses suction filtration separate mode, precipitation and liquid portion is separated, and filter cake, after washing, is put into vacuum drying oven and dried, both obtained boehmite powder; Then by liquid mixture through stratification, collect the dimethyl phthalate of bottom, add siccative (such as anhydrous magnesium sulfate) and dewater, comparatively pure dimethyl phthalate can be obtained, can reuse.Water in above sepn process, essence is the aqueous solution of ammonium chloride, has effect of nitrogenous fertilizer, is thrown in environment on a small quantity, can not pollute.When industrial scale is larger, through reverse osmosis membrane separation operation after can collecting, penetrating fluid is a large amount of pure water, can be used for the preparation of aluminum salt solution, recycle, meanwhile, can also obtain the ammonium chloride solution concentrated, and whole process is without outer pollution discharging thing.
Summary of the invention
The object of the present invention is to provide a kind of with aluminum salt solution and urea for reaction raw materials, utilize the callable sandwich solvent-thermal method of solvent to prepare the method for different-shape boehmite superfine powder.
For achieving the above object, the technical solution used in the present invention is:
1) first, by analytically pure aluminium salt, add in deionized water, magnetic stirring apparatus stirs and makes it dissolve, obtained Al
3+concentration is the clear solution A of 0.1 ~ 0.4mol/L; Aluminium salt can be the one in aluminum chloride, aluminum nitrate, Tai-Ace S 150;
2) add a certain amount of precipitation agent, the 100%-150% of precipitation agent consumption theoretical amount needed for the whole aluminum ion of precipitation, continues to stir half an hour, obtained clear solution B; Precipitation agent refers to urea;
3) in the hydrothermal reaction kettle inner bag of tetrafluoroethylene material, add a certain amount of phthalic ester and form bottom, by the inwall along inner bag careful for a certain amount of solution B, slowly join phthalic acid ester layer top as water layer; Phthalic ester refers to the one in dimethyl phthalate, diethyl phthalate, dibutyl phthalate;
4) by the inwall along inner bag careful for a certain amount of alcohol, slowly join the top of water layer as top layer, total compactedness controls 70 ~ 80%, sealing hydrothermal reaction kettle, put it in electric heating constant-temperature blowing drying box, control at 150-200 DEG C by solvent thermal temperature, reaction 12-24 hour, naturally cools to room temperature after reaction terminates.Alcohol refers to the one in Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol.
5) last, open hydrothermal reaction kettle, first whole upper stratas organic solvent and a small amount of water layer is taken out with glue head dropper, (there is layering in stratification, represent that upper strata organic solvent layer is all taken out), the organic solvent on upper strata is transferred to the Erlenmeyer flask of band stopper, adds siccative and dewater, comparatively pure alcohol can be obtained, can reuse.Siccative refers to anhydrous magnesium sulfate;
6) reaction container bottom is the mixture of boehmite powder, phthalic ester and water layer, first use suction filtration separate mode, precipitation and liquid portion are separated, filter cake is after washing, be placed in the vacuum drying oven inner drying 4 ~ 8 hours of 80-100 DEG C, can boehmite powder be obtained;
7) by liquid mixture through stratification, collect the phthalic ester of bottom, add siccative and dewater, comparatively pure phthalic ester can be obtained, can reuse.Siccative refers to anhydrous magnesium sulfate;
8) water in sepn process, essence is the aqueous solution of ammonium chloride, ammonium nitrate or ammonium sulfate, has effect of nitrogenous fertilizer, be thrown on a small quantity in environment, can not pollute, when industrial scale is larger, through reverse osmosis membrane separation operation after can collecting, penetrating fluid is a large amount of pure water, can be used for the preparation of aluminum salt solution, recycle, simultaneously, can also obtain the ammonium chloride, ammonium nitrate or the ammoniumsulphate soln that concentrate, whole process is without outer pollution discharging thing.
The present invention utilizes the water-soluble of different solvents and boiling point, density variation, separates different organic solvent layers with water layer, devises a kind of sandwich solvent thermal reaction system, achieves solvent callable boehmite powder solvent thermal preparation process.Because in this reaction process, solvent is isolated mutually, reclaim easy, can realize after simple process recycling, reaction process without outer pollution discharging thing, environmental friendliness; The powder produced between the reaction period is deposited in the organic solvent of bottom, completely isolated with water, contributes to the hard aggregation eliminating powder, improves its dispersiveness; Reaction raw materials is cheap and easy to get, and without the need to additive, the morphology microstructure rule of preparation is a kind of green chemistry process process having applications well prospect.
Accompanying drawing explanation
Scanning electron microscope (SEM) photo of accompanying drawing 1 pencil aggregate pattern boehmite superfine powder I
X-ray diffraction (XRD) figure of accompanying drawing 2 pencil aggregate pattern superfine powder II
Scanning electron microscope (SEM) photo of accompanying drawing 3 sheet aggregate pattern boehmite superfine powder III
Scanning electron microscope (SEM) photo of accompanying drawing 4 boehmite superfine powder of core-shell structure V
Scanning electron microscope (SEM) photo of accompanying drawing 5 hollow ball shell pattern boehmite superfine powder VI
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment 1
First, by analytically pure AlCl
39H
2o adds in deionized water, magnetic stirring apparatus stirs and makes it dissolve, obtained Al
3+concentration is the clear solution A of 0.2mol/L; Secondly, add a certain amount of analytically pure urea as precipitation agent, the add-on of urea is the whole Al of precipitation
3+125% of required theory demands amount, continues to stir half an hour, obtained clear solution B; Then, in the hydrothermal reaction kettle inner bag (volume is about 50ml) of tetrafluoroethylene material, the dimethyl phthalate adding 15ml forms bottom, by the inwall along inner bag careful for the solution B of 10ml, slowly joins dimethyl phthalate layer top as water layer; Then, by the inwall along inner bag careful for the n-hexyl alcohol of 15ml, slowly join the top of water layer as top layer, total compactedness controls 80%, sealing hydrothermal reaction kettle, puts it in electric heating constant-temperature blowing drying box, solvent thermal temperature is controlled at 180 DEG C, react 16 hours, after reaction terminates, naturally cool to room temperature; Finally, open hydrothermal reaction kettle, first take out whole upper stratas organic solvent and a small amount of water layer with glue head dropper, (there is layering in stratification, represent that upper strata organic solvent layer is all taken out), the organic solvent on upper strata is transferred to the Erlenmeyer flask of band stopper, adds anhydrous magnesium sulfate drying agent and dewater, comparatively pure n-hexyl alcohol can be obtained, can reuse; Reaction container bottom is the mixture of boehmite powder, dimethyl phthalate and water layer, first use suction filtration separate mode, precipitation and liquid portion are separated, filter cake is after washing, be placed in the vacuum drying oven inner drying 8 hours of 80 DEG C, pencil aggregate pattern boehmite powder can be obtained; Again by liquid mixture through stratification, collect the dimethyl phthalate of bottom, add anhydrous magnesium sulfate drying agent and dewater, comparatively pure dimethyl phthalate can be obtained, can reuse; Remaining water in sepn process, essence is the aqueous solution of ammonium chloride, has effect of nitrogenous fertilizer, is discharged in environment on a small quantity, can not pollute.When industrial scale is larger, through the process of reverse osmosis membrane separation operation after can collecting, penetrating fluid is a large amount of pure water, can be used for preparing aluminum salt solution, and recycle, meanwhile, can also obtain the ammonium chloride solution concentrated, and whole process is without outer pollution discharging thing.
Scanning electron microscope (SEM) photo of the pencil aggregate pattern boehmite superfine powder I that the present embodiment obtains as shown in Figure 1.
Embodiment 2
First, by analytically pure AlCl
39H
2o adds in deionized water, magnetic stirring apparatus stirs and makes it dissolve, obtained Al
3+concentration is the clear solution A of 0.4mol/L; Secondly, add a certain amount of analytically pure urea as precipitation agent, the add-on of urea is the whole Al of precipitation
3+150% of required theory demands amount, continues to stir half an hour, obtained clear solution B; Then, in the hydrothermal reaction kettle inner bag (volume is about 50ml) of tetrafluoroethylene material, the dibutyl phthalate adding 15ml forms bottom, by the inwall along inner bag careful for the solution B of 10ml, slowly joins dibutyl phthalate layer top as water layer; Then, by the inwall along inner bag careful for the Pentyl alcohol of 10ml, slowly join the top of water layer as top layer, total compactedness controls 70%, sealing hydrothermal reaction kettle, puts it in electric heating constant-temperature blowing drying box, solvent thermal temperature is controlled at 150 DEG C, react 24 hours, after reaction terminates, naturally cool to room temperature; Finally, open hydrothermal reaction kettle, first take out whole upper stratas organic solvent and a small amount of water layer with glue head dropper, (there is layering in stratification, represent that upper strata organic solvent layer is all taken out), the organic solvent on upper strata is transferred to the Erlenmeyer flask of band stopper, adds anhydrous magnesium sulfate drying agent and dewater, comparatively pure Pentyl alcohol can be obtained, can reuse; Reaction container bottom is the mixture of boehmite powder, dibutyl phthalate and water layer, first use suction filtration separate mode, precipitation and liquid portion are separated, filter cake is after washing, be placed in the vacuum drying oven inner drying 7 hours of 90 DEG C, pencil aggregate pattern boehmite powder can be obtained; Again by liquid mixture through stratification, collect the dibutyl phthalate of bottom, add anhydrous magnesium sulfate drying agent and dewater, comparatively pure dibutyl phthalate can be obtained, can reuse; Remaining water in sepn process, essence is the aqueous solution of ammonium chloride, has effect of nitrogenous fertilizer, is discharged in environment on a small quantity, can not pollute.When industrial scale is larger, through the process of reverse osmosis membrane separation operation after can collecting, penetrating fluid is a large amount of pure water, can be used for preparing aluminum salt solution, and recycle, meanwhile, can also obtain the ammonium chloride solution concentrated, and whole process is without outer pollution discharging thing.
Fig. 2 is X-ray diffraction (XRD) figure of the pencil aggregate pattern superfine powder II that the present embodiment obtains.Through contrasting with the standard diffraction card of numbering PDF21-1307, confirm that the pencil aggregate pattern superfine powder II that the present embodiment obtains is boehmite.
Embodiment 3
First, by analytically pure Al (NO
3)
39H
2o adds in deionized water, magnetic stirring apparatus stirs and makes it dissolve, obtained Al
3+concentration is the clear solution A of 0.1mol/L; Secondly, add a certain amount of analytically pure urea as precipitation agent, the add-on of urea is the whole Al of precipitation
3+125% of required theory demands amount, continues to stir half an hour, obtained clear solution B; Then, in the hydrothermal reaction kettle inner bag (volume is about 50ml) of tetrafluoroethylene material, the dimethyl phthalate adding 15ml forms bottom, by the inwall along inner bag careful for the solution B of 10ml, slowly joins dimethyl phthalate layer top as water layer; Then, by the inwall along inner bag careful for the n-hexyl alcohol of 11ml, slowly join the top of water layer as top layer, total compactedness controls 72%, sealing hydrothermal reaction kettle, puts it in electric heating constant-temperature blowing drying box, solvent thermal temperature is controlled at 160 DEG C, react 20 hours, after reaction terminates, naturally cool to room temperature; Finally, open hydrothermal reaction kettle, first take out whole upper stratas organic solvent and a small amount of water layer with glue head dropper, (there is layering in stratification, represent that upper strata organic solvent layer is all taken out), the organic solvent on upper strata is transferred to the Erlenmeyer flask of band stopper, adds anhydrous magnesium sulfate drying agent and dewater, comparatively pure n-hexyl alcohol can be obtained, can reuse; Reaction container bottom is the mixture of boehmite powder, dimethyl phthalate and water layer, first use suction filtration separate mode, precipitation and liquid portion are separated, filter cake is after washing, be placed in the vacuum drying oven inner drying 4 hours of 100 DEG C, sheet aggregate pattern boehmite powder can be obtained; Again by liquid mixture through stratification, collect the dimethyl phthalate of bottom, add anhydrous magnesium sulfate drying agent and dewater, comparatively pure dimethyl phthalate can be obtained, can reuse; Remaining water in sepn process, essence is the aqueous solution of ammonium nitrate, has effect of nitrogenous fertilizer, is discharged in environment on a small quantity, can not pollute.When industrial scale is larger, through the process of reverse osmosis membrane separation operation after can collecting, penetrating fluid is a large amount of pure water, can be used for preparing aluminum salt solution, and recycle, meanwhile, can also obtain the ammonium nitrate solution concentrated, and whole process is without outer pollution discharging thing.
Scanning electron microscope (SEM) photo of the sheet aggregate pattern boehmite superfine powder III that the present embodiment obtains as shown in Figure 3.
Embodiment 4
First, by analytically pure Al (NO
3)
39H
2o adds in deionized water, magnetic stirring apparatus stirs and makes it dissolve, obtained Al
3+concentration is the clear solution A of 0.2mol/L; Secondly, add a certain amount of analytically pure urea as precipitation agent, the add-on of urea is the whole Al of precipitation
3+150% of required theory demands amount, continues to stir half an hour, obtained clear solution B; Then, in the hydrothermal reaction kettle inner bag (volume is about 50ml) of tetrafluoroethylene material, the diethyl phthalate adding 12ml forms bottom, by the inwall along inner bag careful for the solution B of 15ml, slowly joins diethyl phthalate layer top as water layer; Then, by the inwall along inner bag careful for the n-Heptyl alcohol of 10ml, slowly join the top of water layer as top layer, total compactedness controls 74%, sealing hydrothermal reaction kettle, puts it in electric heating constant-temperature blowing drying box, solvent thermal temperature is controlled at 180 DEG C, react 16 hours, after reaction terminates, naturally cool to room temperature; Finally, open hydrothermal reaction kettle, first take out whole upper stratas organic solvent and a small amount of water layer with glue head dropper, (there is layering in stratification, represent that upper strata organic solvent layer is all taken out), the organic solvent on upper strata is transferred to the Erlenmeyer flask of band stopper, adds anhydrous magnesium sulfate drying agent and dewater, comparatively pure n-Heptyl alcohol can be obtained, can reuse; Reaction container bottom is the mixture of boehmite powder, diethyl phthalate and water layer, first use suction filtration separate mode, precipitation and liquid portion are separated, filter cake is after washing, be placed in the vacuum drying oven inner drying 8 hours of 80 DEG C, sheet aggregate pattern boehmite powder can be obtained; Again by liquid mixture through stratification, collect the diethyl phthalate of bottom, add anhydrous magnesium sulfate drying agent and dewater, comparatively pure diethyl phthalate can be obtained, can reuse; Remaining water in sepn process, essence is the aqueous solution of ammonium nitrate, has effect of nitrogenous fertilizer, is discharged in environment on a small quantity, can not pollute.When industrial scale is larger, through the process of reverse osmosis membrane separation operation after can collecting, penetrating fluid is a large amount of pure water, can be used for preparing aluminum salt solution, and recycle, meanwhile, can also obtain the ammonium nitrate solution concentrated, and whole process is without outer pollution discharging thing.
Embodiment 5
First, by analytically pure Al
2(SO
4)
318H
2o adds in deionized water, magnetic stirring apparatus stirs and makes it dissolve, obtained Al
3+concentration is the clear solution A of 0.1mol/L; Secondly, add a certain amount of analytically pure urea as precipitation agent, the add-on of urea is the whole Al of precipitation
3+100% of required theory demands amount, continues to stir half an hour, obtained clear solution B; Then, in the hydrothermal reaction kettle inner bag (volume is about 50ml) of tetrafluoroethylene material, the dimethyl phthalate adding 15ml forms bottom, by the inwall along inner bag careful for the solution B of 15ml, slowly joins dimethyl phthalate layer top as water layer; Then, by the inwall along inner bag careful for the n-hexyl alcohol of 10ml, slowly join the top of water layer as top layer, total compactedness controls 80%, sealing hydrothermal reaction kettle, puts it in electric heating constant-temperature blowing drying box, solvent thermal temperature is controlled at 200 DEG C, react 12 hours, after reaction terminates, naturally cool to room temperature; Finally, open hydrothermal reaction kettle, first take out whole upper stratas organic solvent and a small amount of water layer with glue head dropper, (there is layering in stratification, represent that upper strata organic solvent layer is all taken out), the organic solvent on upper strata is transferred to the Erlenmeyer flask of band stopper, adds anhydrous magnesium sulfate drying agent and dewater, comparatively pure n-hexyl alcohol can be obtained, can reuse; Reaction container bottom is the mixture of boehmite powder, dimethyl phthalate and water layer, first use suction filtration separate mode, precipitation and liquid portion are separated, filter cake is after washing, be placed in the vacuum drying oven inner drying 8 hours of 80 DEG C, core-shell structural boehmite powder can be obtained; Again by liquid mixture through stratification, collect the dimethyl phthalate of bottom, add anhydrous magnesium sulfate drying agent and dewater, comparatively pure dimethyl phthalate can be obtained, can reuse; Remaining water in sepn process, essence is the aqueous solution of ammonium sulfate, has effect of nitrogenous fertilizer, is discharged in environment on a small quantity, can not pollute.When industrial scale is larger, through the process of reverse osmosis membrane separation operation after can collecting, penetrating fluid is a large amount of pure water, can be used for preparing aluminum salt solution, and recycle, meanwhile, can also obtain the ammoniumsulphate soln concentrated, and whole process is without outer pollution discharging thing.
Scanning electron microscope (SEM) photo of the boehmite superfine powder of core-shell structure V that the present embodiment obtains as shown in Figure 4.
Embodiment 6
First, by analytically pure Al
2(SO
4)
318H
2o adds in deionized water, magnetic stirring apparatus stirs and makes it dissolve, obtained Al
3+concentration is the clear solution A of 0.3mol/L; Secondly, add a certain amount of analytically pure urea as precipitation agent, the add-on of urea is the whole Al of precipitation
3+125% of required theory demands amount, continues to stir half an hour, obtained clear solution B; Then, in the hydrothermal reaction kettle inner bag (volume is about 50ml) of tetrafluoroethylene material, the dibutyl phthalate adding 10ml forms bottom, by the inwall along inner bag careful for the solution B of 15ml, slowly joins dibutyl phthalate layer top as water layer; Then, by the inwall along inner bag careful for the Pentyl alcohol of 13ml, slowly join the top of water layer as top layer, total compactedness controls 76%, sealing hydrothermal reaction kettle, puts it in electric heating constant-temperature blowing drying box, solvent thermal temperature is controlled at 150 DEG C, react 24 hours, after reaction terminates, naturally cool to room temperature; Finally, open hydrothermal reaction kettle, first take out whole upper stratas organic solvent and a small amount of water layer with glue head dropper, (there is layering in stratification, represent that upper strata organic solvent layer is all taken out), the organic solvent on upper strata is transferred to the Erlenmeyer flask of band stopper, adds anhydrous magnesium sulfate drying agent and dewater, comparatively pure Pentyl alcohol can be obtained, can reuse; Reaction container bottom is the mixture of boehmite powder, dibutyl phthalate and water layer, first use suction filtration separate mode, precipitation and liquid portion are separated, filter cake is after washing, be placed in the vacuum drying oven inner drying 8 hours of 80 DEG C, hollow ball shell pattern boehmite powder can be obtained; Again by liquid mixture through stratification, collect the dibutyl phthalate of bottom, add anhydrous magnesium sulfate drying agent and dewater, comparatively pure dibutyl phthalate can be obtained, can reuse; Remaining water in sepn process, essence is the aqueous solution of ammonium sulfate, has effect of nitrogenous fertilizer, is discharged in environment on a small quantity, can not pollute.When industrial scale is larger, through the process of reverse osmosis membrane separation operation after can collecting, penetrating fluid is a large amount of pure water, can be used for preparing aluminum salt solution, and recycle, meanwhile, can also obtain the ammoniumsulphate soln concentrated, and whole process is without outer pollution discharging thing.
Scanning electron microscope (SEM) photo of the hollow ball shell pattern boehmite superfine powder VI that the present embodiment obtains as shown in Figure 5.
Claims (2)
1. prepare a sandwich solvent-thermal process method for boehmite powder, it is characterized in that, this sandwich solvent-thermal process method preparing boehmite powder comprises the following steps:
1) first, by analytically pure aluminium salt, add in deionized water, magnetic stirring apparatus stirs and makes it dissolve, obtained Al
3+concentration is the clear solution A of 0.1 ~ 0.4mol/L;
2) add a certain amount of precipitation agent, the 100%-150% of precipitation agent consumption theoretical amount needed for the whole aluminum ion of precipitation, continue to stir half an hour, obtained clear solution B, described precipitation agent refers to urea;
3) in the hydrothermal reaction kettle inner bag of tetrafluoroethylene material, add a certain amount of phthalic ester and form bottom, by the inwall along inner bag careful for a certain amount of solution B, slowly join phthalic acid ester layer top as water layer;
4) by the inwall along inner bag careful for a certain amount of alcohol, slowly join the top of water layer as top layer, total compactedness controls 70 ~ 80%, sealing hydrothermal reaction kettle, put it in electric heating constant-temperature blowing drying box, solvent thermal temperature is controlled at 150-200 DEG C, reaction 12-24 hour, naturally cool to room temperature after reaction terminates, described alcohol refers to the one in Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol;
5) last, open hydrothermal reaction kettle, first whole upper stratas organic solvent and a small amount of water layer is taken out with glue head dropper, stratification, the organic solvent on upper strata is transferred to the Erlenmeyer flask of band stopper, adds siccative and dewater, obtain comparatively pure alcohol, realize recycling, described siccative refers to anhydrous magnesium sulfate;
6) reaction container bottom is the mixture of boehmite powder, phthalic ester and water layer, first use suction filtration separate mode, precipitation and liquid portion are separated, filter cake is after washing, be placed in the vacuum drying oven inner drying 4 ~ 8 hours of 80-100 DEG C, obtain boehmite powder;
7) by liquid mixture through stratification, collect the phthalic ester of bottom, add siccative and dewater, obtain comparatively pure phthalic ester, realize recycling, described siccative refers to anhydrous magnesium sulfate;
8) water in sepn process, essence is the aqueous solution of ammonium chloride, ammonium nitrate or ammonium sulfate, has effect of nitrogenous fertilizer, be thrown on a small quantity in environment, can not pollute, when industrial scale is larger, through reverse osmosis membrane separation operation after collection, penetrating fluid is a large amount of pure water, for the configuration of aluminum salt solution, realize recycle, simultaneously, also obtain the ammonium chloride, ammonium nitrate or the ammoniumsulphate soln that concentrate, whole process is without outer pollution discharging thing.
2. prepare the sandwich solvent-thermal process method of boehmite powder as claimed in claim 1, it is characterized in that: aluminium salt is the one in aluminum chloride, aluminum nitrate, Tai-Ace S 150; Phthalic ester refers to the one in dimethyl phthalate, diethyl phthalate, dibutyl phthalate.
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| CN102701244A (en) * | 2012-07-02 | 2012-10-03 | 泰山医学院 | Method and device for controlling morphology of boehmite |
| CN102701245A (en) * | 2012-07-02 | 2012-10-03 | 泰山医学院 | Method and device for preparing boehmite superfine powder of core-shell structure |
| CN102730726A (en) * | 2012-07-02 | 2012-10-17 | 泰山医学院 | Method and device for preparing boehmite powder by using esterification reaction hydrothermal method |
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| CN102701244A (en) * | 2012-07-02 | 2012-10-03 | 泰山医学院 | Method and device for controlling morphology of boehmite |
| CN102701245A (en) * | 2012-07-02 | 2012-10-03 | 泰山医学院 | Method and device for preparing boehmite superfine powder of core-shell structure |
| CN102730726A (en) * | 2012-07-02 | 2012-10-17 | 泰山医学院 | Method and device for preparing boehmite powder by using esterification reaction hydrothermal method |
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