CN103011219A - Mesoporous alumina and preparation method thereof - Google Patents
Mesoporous alumina and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a mesoporous alumina The preparation method comprises the following steps of: removing impurities of a mineral resource containing alumina; transforming the alumium into meta-aluminate, separating from impurity ions, and regulating a pH value by an acid, so the meta-aluminate is turned into a boehmite precipitate; filtering and collecting the precipitate and taking as an aluminum source; mixing the obtained boehmite precipitate with a template agent and water in the ratio of 1: (0.02-0.5): (20-70) by amounts of the materials, regulating the pH value to 3-10, and aging for at least 6h at 20-120 DEG C, wherein the template agent is triton X-100 and/or cetyl trimethyl ammonium bromide (CTAB); removing impurities of the aged mixture, to obtain a solid product; and baking for at least 1.5h at 450-950 DEG C, to obtain the mesoporous alumina. The preparation method disclosed by the invention has the characteristics that the operation is simple; the iron-free mesoporous alumina is prepared under a moderate condition by adding an iron removal process in the preparation process; and the mesoporous alumina can maintain the mesoporous structure after being baked, and has comparatively high specific surface area.
Description
Technical field
The present invention relates to field of inorganic material preparing technology, particularly, the present invention relates to a kind of meso-porous alumina and preparation method thereof.
Background technology
Meso-porous alumina has the duct of higher specific surface area, narrower pore size distribution and homogeneous and is widely used as sorbent material, catalyzer and support of the catalyst.At present, patent and bibliographical information about the meso-porous alumina preparation are existing many, such as CN102219242A, and CN101024503A, CN 101993102A, CN 101597077A, CN102219243A all with inorganic aluminate as aluminium Yanyuan such as aluminum nitrate, aluminum chloride and Tai-Ace S 150, respectively with P123, Macrogol 1540, methylcellulose gum, amino acid type surfactant, glucose are that template prepares meso-porous alumina; CN101829552A is take aluminum nitrate as the aluminium source, take CTAB as masterplate, the preparation meso-porous alumina, it has adopted organic solvent, and cost is higher, there is potential safety hazard, simultaneous reactions adopts autoclave, and temperature of reaction is higher, and energy consumption is higher, and the meso-porous alumina specific surface area of preparation is large not, can not satisfy the demand.CN101372342A, CN1958450A adopt respectively the organoaluminum source, ionic liquid, and the straight-chain carboxylic acid prepares meso-porous alumina for template.(HoSeok Park, et al., the Chem.Mater.2007 such as HoSeok Park, 19,535-542) with aluminum isopropylate as the aluminium source, ionic liquid at room temperature C16MimCl is as template, synthesize the large pore volume meso-porous alumina, the aperture of products obtained therefrom is 9.9nm, and pore volume is 1.46cm
3/ g.MingzhuLiu and Huaming Yang(Mingzhu Liu and Huaming Yan, Colloids and Surfaces A:Physicochem.Eng.Aspects 371 (2010) 126-130) take aluminum nitrate as the aluminium source, P123 prepares macropore and composite mesoporous aluminum oxide as template.But the meso-porous alumina of prior art preparation exists specific surface area large not, can't satisfy existing needs, perhaps the problem such as preparation method's complexity.
The natural mineral resource that contains aluminum oxide mainly contains kaolin, nakrite, wilkinite, agalmatolite (Al
2O
3〉=16%), montmorillonite, dikite (contain Al
2O
325%-30%), halloysite (Al
2O
3Be about 37.3%), culm clay, clay and coal gangue (Al
2O
3Be about 16~36%) etc.These mineral wealth have reserves than horn of plenty in China, and alumina content is approximately 16~37.3%.But major part still is in the elementary process segment; Wherein also have the part mineral to stack with the form of waste, take coal gangue as example, coal gangue is the solid waste that discharges in coal mining process and the coal washing process, has accumulated over the years about 1,000,000,000 tons of coal gangue, and still continues to discharge about 100,000,000 tons every year.Its main component is Al
2O
3, SiO
2, Al
2O
3Content is about 16~36%.Therefore, the natural mineral that is rich in aluminum oxide such as coal gangue can be used as the raw material of producing meso-porous alumina.
The patent report for preparing aluminum oxide take salic natural mineral resource as raw material is existing many, such as patent CN102180493A, CN101857251A, CN101172632A, CN1281820A, CN101857230A, CN102180491A, CN101759209A, CN1915829A, CN101234774A, CN101450811A etc., but based on take salic natural mineral resource as raw material, document through the report of preparation meso-porous alumina after the pre-treatment is few in number, (J.Mater.Chem., 1995 such as Okada, 5 (8), 1241-1244.J.Mater.Chem., 1997,7 (8), 1615-1621.J.Mater.Chem., 1998,8, the 2863-2867) kaolin after the employing alkaline purification roasting, (the Ind.Eng.Chem.Res.2011 such as Yu zhanglong, 50,8524-8528.) adopt citric acid leaching metakaolin, take ammoniacal liquor as pH adjusting agent, add bicarbonate of ammonia, then preparation aluminium carbonate ammonium intermediate carries out temperature-programmed calcination aluminium carbonate ammonium intermediate, obtains meso-porous alumina.
Make a general survey of bibliographical information, mainly prepare meso-porous alumina with organoaluminum or inorganic aluminum chemical industry raw material as the aluminium source, and with natural mineral raw basically for the preparation of common aluminum oxide.
Therefore, develop a kind of take natural mineral as raw material, the preparation method is simple, the meso-porous alumina that obtains bigger serface, even aperture distribution is an affiliated art difficult problem.
Summary of the invention
For the deficiencies in the prior art, one of purpose of the present invention is to provide a kind of preparation method of meso-porous alumina.Described method is take salic natural mineral as raw material, get in conjunction with the removal of impurities operation with acidleach, prepare meso-porous alumina take non-ionic type template triton x-100 as template, prepare the large pore volume meso-porous alumina take ionic template cetyl trimethylammonium bromide (CTAB) as template.
It is that raw material prepares meso-porous alumina that the present invention adopts the natural mineral resource of aluminum oxide, realizes the high value added utilization of non-metallic minerals resource.
Said method comprising the steps of:
(1) will contain the mineral wealth removal of impurities of aluminum oxide, and aluminium will be converted into meta-aluminate, separate with foreign ion, use acid for adjusting pH, be precipitated, collecting precipitation material and as the aluminium source;
(2) throw out, template and the water that step (1) are obtained are 1:(0.02 ~ 0.5 by molar ratio): mix (20 ~ 70), regulating pH is 3 ~ 10,20 ~ 120 ℃ of ageings at least 6 hours, wherein said template was triton x-100 and/or cetyl trimethylammonium bromide;
(3) with the mixture removal of impurities that obtains after step (2) ageing, obtain solid product, then 450 ~ 950 ℃ of roastings at least 1.5 hours, obtain meso-porous alumina.
The extraction that step (1) is described to contain meta-aluminate in the mineral wealth of aluminum oxide can be adopted existing techniques in realizing, and one of ordinary skill in the art can select according to actual needs.
Preferably, described step (1) comprising:
The mineral wealth that (11) will contain aluminum oxide are crushed to powder, roasting; By roasting, the mineral that will contain aluminum oxide obtain activation and become active condition, in roasting process, utilize the dehydration, decomposition etc. of mineral to make atom or interionicly increase in conjunction with destroyed or surface-area, and make it be in unsettled active condition, increased its chemical reaction ability, be conducive to the leaching reaction and carry out; The purpose of roasting is to improve the chemical reactivity of material; The temperature of roasting, time are relevant with the granularity of baking modes and roasting material, and the fluosolids roasting time is shorter than fixed bed roasting time, and fine granular materials is shorter than group granule materials roasting time;
(12) the powder leaching after adopting acid solution to roasting separates liquid phase and solid phase;
(13) in the liquid phase that step (12) obtains, add alkali, make aluminium be converted into meta-aluminate, and the foreign ions such as iron, magnesium form throw out, remove throw out, obtain meta-aluminate solution;
(14) regulate pH, make the meta-aluminate precipitation, to the throw out removal of impurities, the throw out that obtains is as the aluminium source.
Preferably, the described mineral wealth that contain aluminum oxide are a kind or at least 2 kinds combination in kaolin, nakrite, wilkinite, agalmatolite, montmorillonite, dikite, halloysite, culm clay, clay or the coal gangue.
Preferably, the described powder granularity of step (11) is less than 150 orders, and such as 160 orders, 170 orders, 250 orders, 300 orders, 400 orders, 500 orders etc. is particularly preferably less than 200 orders.
Preferably, the described maturing temperature of step (11) is 450 ~ 1000 ℃, more preferably 470 ~ 950 ℃, is particularly preferably 500 ~ 900 ℃.
Preferably, the described roasting time of step (11) is at least 0.1 hour, such as 0.11 hour, 0.12 hour, 0.2 hour, 0.3 hour, 0.4 hour, 0.5 hour, 1 hour, 2 hours, 3 hours, 5 hours, 7 hours, 7.5 hours, 7.8 hours, 7.9 hours etc., more preferably 0.1 ~ 8 hour, more preferably 0.1 ~ 6 hour, be particularly preferably 0.1 ~ 4 hour.
Preferably, step (12) is described is separated into filtration.
Preferably, the described acid of step (12) is a kind or at least 2 kinds combination in hydrochloric acid, sulfuric acid or the nitric acid.
Preferably, the described leaching temperature of step (12) is 50 ~ 150 ℃, more preferably 60 ~ 130 ℃, is particularly preferably 70 ~ 120 ℃.
Preferably, the described leaching time of step (12) is at least 0.5 hour, more preferably 0.8 ~ 10 hour, is particularly preferably 1 ~ 6 hour.
Preferably, step (13) is removed throw out by filtering.
Preferably, the described alkali of step (13) is sodium hydroxide and/or potassium hydroxide.
Preferably, the described removal of impurities of step (14) is filtration, then washing precipitate.
Preferably, the terminal point of the described adjusting of step (14) pH is 7 ~ 9.
Preferably, the described template of step (2) is triton x-100 or cetyl trimethylammonium bromide (CTAB); In the present invention, the pore size distribution of the meso-porous alumina that obtains take triton x-100 as template is 4.58 ~ 6.25nm, and specific surface area is 140 ~ 290m
2/ g, pore volume are 0.29 ~ 0.60cm
3/ g; Obtain the large pore volume meso-porous alumina take cetyl trimethylammonium bromide as template, its pore size distribution is 7.58 ~ 12.9nm, and specific surface area is 253 ~ 358m
2/ g, pore volume are 1.24 ~ 1.75cm
3/ g.
Preferably, the molar ratio of the described throw out of step (2), template and water is 1:(0.04 ~ 0.4): (25 ~ 65) are particularly preferably 1:(0.06 ~ 0.3): (30 ~ 60).
Preferably, the described pH of step (2) is 3.5 ~ 9.5, is particularly preferably 4 ~ 9.
Preferably, the described Aging Temperature of step (2) is 25 ~ 110 ℃, is particularly preferably 30 ~ 100 ℃.
Preferably, the described digestion time of step (2) is 8 ~ 90 hours, is particularly preferably 10 ~ 72 hours.
Preferably, the described water of step (2) is deionized water.
Stir when preferably, step (2) is regulated pH.
Preferably, the described removal of impurities of step (3) comprises filtration successively, washing, drying.
Preferably, the described maturing temperature of step (3) is 480 ~ 900 ℃, more preferably 500 ~ 800 ℃, is particularly preferably 550 ~ 700 ℃.
Preferably, the described roasting time of step (3) is 1.8 ~ 8 hours, is particularly preferably 2 ~ 6 hours.
Described triton x-100 is the octyl phenyl Soxylat A 25-7, is broad-spectrum nonionogenic tenside, and one of ordinary skill in the art can by commercially available acquisition, also can adopt prior art/new technology to prepare.
Utilize natural mineral resource to prepare molecular screen material, have obvious advantage with low cost, be subject to extensive concern.Such as, coal gangue is the solid by the mineral composition that contains silicon oxide and aluminum oxide, it is the solid waste of rejecting in the progress of coal mining, to pose a big pressure to environment.The coal gangue main chemical compositions is Al
2O
3, SiO
2, the aluminium source of synthesising mesoporous aluminum oxide can be provided.
One of purpose of the present invention also is to provide a kind of meso-porous alumina, and described meso-porous alumina is prepared by aforesaid method.In the present invention, the pore size distribution of the meso-porous alumina that obtains take triton x-100 as template is 4.58 ~ 6.25nm, and specific surface area is 140 ~ 290m
2/ g, pore volume are 0.29 ~ 0.60cm
3/ g; Obtain the large pore volume meso-porous alumina take cetyl trimethylammonium bromide as template, its pore size distribution is 7.58 ~ 12.9nm, and specific surface area is 253 ~ 358m
2/ g, pore volume are 1.24 ~ 1.75cm
3/ g.
The present invention has following characteristics:
1) adopting natural aluminum-containing mineral resource is raw material, has both solved the problem of the contaminate environment of some solid waste, can promote again the added value of these mineral;
2) in the preparation process in conjunction with impurity removal process, such as impurity such as iron, magnesium and calcium, obtain the higher meso-porous alumina of purity, thereby improved the using value of meso-porous alumina;
3) prepared large pore volume meso-porous alumina has large pore volume and wide aperture take mineral as raw material, will have great importance aspect catalysis or the absorption;
4) preparation technology is simple, and operational condition is controlled easily, and cost compare is low.
Description of drawings
Fig. 1 is the process flow sheet of one embodiment of the invention;
Fig. 2 is the meso-porous alumina small-angle diffraction collection of illustrative plates of the embodiment of the invention 1 preparation;
Fig. 3 is the meso-porous alumina wide-angle diffracting spectrum of the embodiment of the invention 2 preparations;
Fig. 4 is the meso-porous alumina nitrogen adsorption desorption curve of the embodiment of the invention 2 preparations;
Fig. 5 is the meso-porous alumina pore size distribution curve of the embodiment of the invention 2 preparations;
Fig. 6 is the meso-porous alumina small-angle diffraction collection of illustrative plates of the embodiment of the invention 3 preparations;
Fig. 7 is the meso-porous alumina wide-angle diffracting spectrum of the embodiment of the invention 4 preparations;
Fig. 8 is the meso-porous alumina small-angle diffraction collection of illustrative plates of the embodiment of the invention 4 preparations;
Fig. 9 is the meso-porous alumina pore size distribution curve of the embodiment of the invention 4 preparations;
Figure 10 is the meso-porous alumina small-angle diffraction collection of illustrative plates of the embodiment of the invention 5 preparations;
Figure 11 is the meso-porous alumina pore size distribution curve of the embodiment of the invention 5 preparations;
Figure 12 is the meso-porous alumina small-angle diffraction collection of illustrative plates of the embodiment of the invention 6 preparations;
Figure 13 is the meso-porous alumina small-angle diffraction collection of illustrative plates of the embodiment of the invention 7 preparations;
Figure 14 is the meso-porous alumina small-angle diffraction collection of illustrative plates of the embodiment of the invention 8 preparations;
Figure 15 is the meso-porous alumina small-angle diffraction collection of illustrative plates of the embodiment of the invention 9 preparations;
Figure 16 is the meso-porous alumina small-angle diffraction collection of illustrative plates of the embodiment of the invention 10 preparations;
Figure 17 is the meso-porous alumina small-angle diffraction collection of illustrative plates of the embodiment of the invention 11 preparations;
Figure 18 is the meso-porous alumina small-angle diffraction collection of illustrative plates of the embodiment of the invention 12 preparations.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand that described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment in this patent all tests as raw material with coal gangue, with this feasibility of the present invention is described.Its chemical ingredients is mainly Al
2O
3And SiO
2, and a small amount of Fe
2O
3, TiO
2, and the K of trace
2O, MgO, CaO, Na
2O, wherein Al
2O
3And SiO
2Content is respectively 45.8% and 37.5%.
Embodiment 1:
The preparation method of meso-porous alumina, its concrete technology Step By Condition is as follows:
(1) with the coal gangue behind the ball milling in 800 ℃ of roastings, be that 6mol/L HCl solution is by solid-to-liquid ratio 1:4.5(g/ml or kg/L with concentration then), in 90 ℃ of stirring and refluxing leaching 2 hours, filter and collect filtrate;
(2) measure the filtrate that 30ml step (1) is collected, add excessive 6.0mol/LNaOH solution, until the Al (OH) that produces
3Precipitation disappears, and is converted into NaAlO fully
2, remove by filter insoluble impurities, collect filtrate for later use;
(3) in the filtrate that step (2) is collected, add 6.0mol/L HCl solution, regulate pH and approach neutrality, make NaAlO
2Be converted into the boehmite precipitation fully, filtration washing is collected filter cake as the aluminium source of preparation meso-porous alumina to neutrality with without NaCl;
(4) filter cake, triton x-100 and deionized water are pressed 1(with Al in the pickling liquor
3+Content meter): the molar ratio of 0.12:52, mixing and stirring, regulating pH with acetum is 4.0, room temperature ageing reaction 48 hours;
(5) filter, 105 ℃ of dry 12h are in 550 ℃ of roasting 6h.
The aperture of the meso-porous alumina that this law makes is 4.58nm, and specific surface area is 289.2m
2/ g, pore volume are 0.59cm
3/ g.Its small-angle diffraction collection of illustrative plates is seen Fig. 2.
Embodiment 2:
The preparation method of meso-porous alumina, its concrete technology Step By Condition is as follows:
(1) with the coal gangue behind the ball milling in 800 ℃ of roastings, then with concentration be 9mol/L HCl solution by solid-to-liquid ratio 1:3.0, in 90 ℃ of stirring and refluxing leaching 2 hours, filter and collect filtrate;
(2) measure the filtrate that 30ml step (1) is collected, add excessive 6.0mol/L KOH solution, until the Al (OH) that produces
3Precipitation disappears, and is converted into KAlO fully
2, remove by filter insoluble impurities, collect filtrate for later use;
(3) in the filtrate that step (2) is collected, add 6.0mol/L H
2SO
4Solution is regulated pH and is approached neutrality, makes KAlO
2Be converted into the boehmite precipitation fully, filtration washing is to neutrality with without K
2SO
4, collect filter cake as the aluminium source of preparation meso-porous alumina;
(4) filter cake, triton x-100 and deionized water are pressed 1(with Al in the pickling liquor
3+Content meter): the molar ratio of 0.06:52, mixing and stirring, regulating pH is 7.0, room temperature ageing reaction 72 hours;
(5) filter, 105 ℃ of dry 12h are in 700 ℃ of roasting 6h.
The aperture of the meso-porous alumina that this law makes is 6.13nm, and specific surface area is 140.6m
2/ g, pore volume are 0.29cm
3/ g.Its wide-angle diffracting spectrum is seen Fig. 3, and nitrogen adsorption desorption curve is seen Fig. 4, and pore size distribution curve is seen Fig. 5.
Embodiment 3:
The preparation method of meso-porous alumina, its concrete technology Step By Condition is as follows:
(1) with the coal gangue behind the ball milling in 900 ℃ of roastings, then with concentration be 6mol/L HCl solution by solid-to-liquid ratio 1:4.5, in 90 ℃ of stirring and refluxing leaching 2 hours, filter and collect filtrate;
(2) measure the filtrate that 30ml step (1) is collected, add excessive 6.0mol/LNaOH solution, until the Al (OH) that produces
3Precipitation disappears, and is converted into NaAlO fully
2, remove by filter insoluble impurities, collect filtrate for later use;
(3) in the filtrate that step (2) is collected, add 6.0mol/L HNO
3Solution is regulated pH and is approached neutrality, makes NaAlO
2Be converted into precipitation fully, the filtration washing filter cake is to not containing NaNO
3, collect filter cake as the aluminium source of preparation meso-porous alumina;
(4) filter cake, triton x-100 and deionized water are pressed 1(with Al in the pickling liquor
3+Content meter): the molar ratio of 0.15:52, mixing and stirring, regulating pH with sodium hydroxide solution is 9.0, changes reactor in 60 ℃ of ageing reactions 72 hours;
(5) filter, 105 ℃ of dry 12h are in 700 ℃ of roasting 6h.
The aperture of the meso-porous alumina that this law makes is 6.15nm, and specific surface area is 231.7m
2/ g, pore volume are 0.60cm
3/ g.Its small-angle diffraction collection of illustrative plates is seen Fig. 6.
Embodiment 4:
The preparation method of meso-porous alumina, its concrete technology Step By Condition is as follows:
(1) with the coal gangue behind the ball milling in 800 ℃ of roastings, then with concentration be 6mol/L HCl solution by solid-to-liquid ratio 1:5.0, in 90 ℃ of stirring and refluxing leaching 3 hours, filter and collect filtrate;
(2) measure the filtrate that 30ml step (1) is collected, add excessive 6.0mol/LNaOH solution, until the Al (OH) that produces
3Precipitation disappears, and is converted into NaAlO fully
2, remove by filter insoluble impurities, collect filtrate for later use;
(3) in the filtrate that step (2) is collected, add 8.0mol/L H
2SO
4Solution is regulated pH and is approached neutrality, makes NaAlO
2Be converted into the boehmite precipitation fully, the filtration washing filter cake is to not containing Na
2SO
4, collect filter cake as the aluminium source of preparation meso-porous alumina;
(4) filter cake, triton x-100 and deionized water are pressed 1(with Al in the pickling liquor
3+Content meter): the molar ratio of 0.03:52, mixing and stirring, regulating pH is 7.0, room temperature ageing reaction 48 hours;
(5) filter, 105 ℃ of dry 12h are in 550 ℃ of roasting 6h.
The aperture of the meso-porous alumina that this law makes is 5.04nm, and specific surface area is 225.0m
2/ g, pore volume are 0.36cm
3/ g.Its wide-angle diffracting spectrum is seen Fig. 7, and the small-angle diffraction collection of illustrative plates is seen Fig. 8, and pore size distribution curve is seen Fig. 9.
Embodiment 5:
The preparation method of meso-porous alumina, its concrete technology Step By Condition is as follows:
(1) with the coal gangue behind the ball milling in 800 ℃ of roastings, then with concentration be 7.5mol/L HCl solution by solid-to-liquid ratio 1:4, in 90 ℃ of stirring and refluxing leaching 2 hours, filter and collect filtrate;
(2) measure the filtrate that 30ml step (1) is collected, add excessive 6.0mol/LNaOH solution, until the Al (OH) that produces
3Precipitation disappears, and is converted into NaAlO fully
2, remove by filter insoluble impurities, collect filtrate for later use;
(3) in the filtrate that step (2) is collected, add 6.0mol/L HCl solution, regulate pH and approach neutrality, make NaAlO
2Be converted into the boehmite precipitation fully, the filtration washing filter cake is collected filter cake as the aluminium source of preparation meso-porous alumina to not containing NaCl;
(4) filter cake, triton x-100 and deionized water are pressed 1(with Al in the pickling liquor
3+Content meter): the molar ratio of 0.06:52, mixing and stirring, regulating pH with dilute hydrochloric acid solution is 5.0,40 ℃ of ageing reactions 48 hours;
(5) filter, 105 ℃ of dry 12h are in 550 ℃ of roasting 6h.
The aperture of the meso-porous alumina that this law makes is 6.25nm, and specific surface area is 243.7m
2/ g, pore volume are 0.41cm
3/ g.Its small-angle diffraction collection of illustrative plates is seen Figure 10, and pore size distribution curve is seen Figure 11.
The preparation method of meso-porous alumina, its concrete technology Step By Condition is as follows:
(1) with the coal gangue behind the ball milling in 450 ℃ of roastings, be that 6mol/L HCl solution is by solid-to-liquid ratio 1:4.5(g/ml or kg/L with concentration then), in 60 ℃ of stirring and refluxing leaching 8 hours, filter and collect filtrate;
(2) measure the filtrate that 30ml step (1) is collected, add excessive 6.0mol/LNaOH solution, until the Al (OH) that produces
3Precipitation disappears, and is converted into NaAlO fully
2, remove by filter insoluble impurities, collect filtrate for later use;
(3) in the filtrate that step (2) is collected, add 6.0mol/L HCl solution, regulate pH and approach neutrality, make NaAlO
2Be converted into the boehmite precipitation fully, filtration washing is collected filter cake as the aluminium source of preparation meso-porous alumina to neutrality with without NaCl;
(4) filter cake, triton x-100 and deionized water are pressed 1(with Al in the pickling liquor
3+Content meter): the molar ratio of 0.4:25, mixing and stirring, regulating pH is 10.0,20 ℃ of ageing reactions 100 hours;
(5) filter, 105 ℃ of dry 12h are in 450 ℃ of roasting 20h.
The aperture of the meso-porous alumina that this law makes is 4.39nm, and specific surface area is 284.6m
2/ g, pore volume are 0.53cm
3/ g.
Embodiment 7:
The preparation method of large pore volume meso-porous alumina, its concrete technology Step By Condition is as follows:
(1) with the Coaseries kaolin behind the ball milling in 800 ℃ of roastings, be that 6mol/L HCl solution is by solid-to-liquid ratio 1:4.5(g/ml or kg/L with concentration then), in 90 ℃ of stirring and refluxing leaching 2 hours, filter and collect filtrate;
(2) measure the filtrate that 30ml step (1) is collected, add excessive 6.0mol/LNaOH solution, until the Al (OH) that produces
3Precipitation disappears, and is converted into NaAlO fully
2, remove by filter insoluble impurities, collect filtrate for later use;
(3) in the filtrate that step (2) is collected, add 6.0mol/L HCl solution, regulate pH and approach neutrality, make NaAlO
2Be converted into the boehmite precipitation fully, filtration washing is collected filter cake as the aluminium source of preparation meso-porous alumina to neutrality with without NaCl;
(4) with filter cake, cetyl trimethylammonium bromide (CTAB) and deionized water by filter cake: cetyl trimethylammonium bromide (CTAB): deionized water is that 1(is with Al in the pickling liquor
3+Content meter): the molar ratio of 0.05:40, mixing and stirring, room temperature ageing reaction 48 hours;
(5) filter, 105 ℃ of dry 12h are in 550 ℃ of roasting 6h.
The aperture of the large pore volume meso-porous alumina that this law makes is 7.58nm, and specific surface area is 344.2m
2/ g, pore volume are 1.47cm
3/ g.Its small-angle diffraction collection of illustrative plates is seen Figure 12.
Embodiment 8:
The preparation method of large pore volume meso-porous alumina, its concrete technology Step By Condition is as follows:
(1) with the Coaseries kaolin behind the ball milling in 800 ℃ of roastings, then with concentration be 9mol/L HCl solution by solid-to-liquid ratio 1:3.0, in 90 ℃ of stirring and refluxing leaching 2 hours, filter and collect filtrate;
(2) measure the filtrate that 30ml step (1) is collected, add excessive 6.0mol/LNaOH solution, until the Al (OH) that produces
3Precipitation disappears, and is converted into NaAlO fully
2, remove by filter insoluble impurities, collect filtrate for later use;
(3) in the filtrate that step (2) is collected, add 6.0mol/L HCl solution, regulate pH and approach neutrality, make NaAlO
2Be converted into the boehmite precipitation fully, filtration washing is collected filter cake as the aluminium source of preparation meso-porous alumina to neutrality with without NaCl;
(4) with filter cake, cetyl trimethylammonium bromide (CTAB) and deionized water by filter cake: cetyl trimethylammonium bromide (CTAB): deionized water is that 1(is with Al in the pickling liquor
3+Content meter): the molar ratio of 0.10:45, mixing and stirring, room temperature ageing reaction 72 hours;
(5) filter, 105 ℃ of dry 12h are in 700 ℃ of roasting 6h.
The aperture of the large pore volume meso-porous alumina that this law makes is 9.76nm, and specific surface area is 334.6m
2/ g, pore volume are 1.245cm
3/ g.Its small-angle diffraction collection of illustrative plates is seen Figure 13.
Embodiment 9:
The preparation method of large pore volume meso-porous alumina, its concrete technology Step By Condition is as follows:
(1) with the Coaseries kaolin behind the ball milling in 900 ℃ of roastings, then with concentration be 6mol/L HCl solution by solid-to-liquid ratio 1:4.5, in 90 ℃ of stirring and refluxing leaching 2 hours, filter and collect filtrate;
(2) measure the filtrate that 30ml step (1) is collected, add excessive 6.0mol/LNaOH solution, until the Al (OH) that produces
3Precipitation disappears, and is converted into NaAlO fully
2, remove by filter insoluble impurities, collect filtrate for later use;
(3) in the filtrate that step (2) is collected, add 6.0mol/L HCl solution, regulate pH and approach neutrality, make NaAlO
2Be converted into precipitation fully, the filtration washing filter cake is collected filter cake as the aluminium source of preparation meso-porous alumina to not containing NaCl;
(4) with filter cake, cetyl trimethylammonium bromide (CTAB) and deionized water by filter cake: cetyl trimethylammonium bromide (CTAB): deionized water is that 1(is with Al in the pickling liquor
3+Content meter): the molar ratio of 0.15:50, mixing and stirring changes reactor in 60 ℃ of ageing reactions 72 hours;
(5) filter, 105 ℃ of dry 12h are in 700 ℃ of roasting 6h.
The aperture of the large pore volume meso-porous alumina that this law makes is 12.9nm, and specific surface area is 253.4m
2/ g, pore volume are 1.487cm
3/ g.Its small-angle diffraction collection of illustrative plates is seen Figure 14.
Embodiment 10:
The preparation method of large pore volume meso-porous alumina, its concrete technology Step By Condition is as follows:
(1) with the Coaseries kaolin behind the ball milling in 800 ℃ of roastings, then with concentration be 6mol/L HCl solution by solid-to-liquid ratio 1:5.0, in 90 ℃ of stirring and refluxing leaching 3 hours, filter and collect filtrate;
(2) measure the filtrate that 30ml step (1) is collected, add excessive 6.0mol/LNaOH solution, until the Al (OH) that produces
3Precipitation disappears, and is converted into NaAlO fully
2, remove by filter insoluble impurities, collect filtrate for later use;
(3) in the filtrate that step (2) is collected, add 6.0mol/L HCl solution, regulate pH and approach neutrality, make NaAlO
2Be converted into the boehmite precipitation fully, the filtration washing filter cake is collected filter cake as the aluminium source of preparation meso-porous alumina to not containing NaCl;
(4) with filter cake, cetyl trimethylammonium bromide (CTAB) and deionized water by filter cake: cetyl trimethylammonium bromide (CTAB): deionized water is that 1(is with Al in the pickling liquor
3+Content meter): the molar ratio of 0.18:35, mixing and stirring, room temperature ageing reaction 72 hours;
(5) filter, 105 ℃ of dry 12h are in 550 ℃ of roasting 6h.
The aperture of the large pore volume meso-porous alumina that this law makes is 10.1nm, and specific surface area is 324.2m
2/ g, pore volume are 1.67cm
3/ g.Its small-angle diffraction collection of illustrative plates is seen Figure 15.
Embodiment 11:
The preparation method of large pore volume meso-porous alumina, its concrete technology Step By Condition is as follows:
(1) with the Coaseries kaolin behind the ball milling in 800 ℃ of roastings, then with concentration be 6mol/L HCl solution by solid-to-liquid ratio 1:5.0, in 90 ℃ of stirring and refluxing leaching 3 hours, filter and collect filtrate;
(2) measure the filtrate that 30ml step (1) is collected, add excessive 6.0mol/LNaOH solution, until the Al (OH) that produces
3Precipitation disappears, and is converted into NaAlO fully
2, remove by filter insoluble impurities, collect filtrate for later use;
(3) in the filtrate that step (2) is collected, add 6.0mol/L HCl solution, regulate pH and approach neutrality, make NaAlO
2Be converted into the boehmite precipitation fully, the filtration washing filter cake is collected filter cake as the aluminium source of preparation meso-porous alumina to not containing NaCl;
(4) with filter cake, cetyl trimethylammonium bromide (CTAB) and deionized water by filter cake: cetyl trimethylammonium bromide (CTAB): deionized water is that 1(is with Al in the pickling liquor
3+Content meter): the molar ratio of 0.18:35, mixing and stirring, room temperature ageing reaction 72 hours;
(5) filter, 105 ℃ of dry 12h are in 700 ℃ of roasting 6h.
The aperture of the large pore volume meso-porous alumina that this law makes is 11.5nm, and specific surface area is 305.53m
2/ g, pore volume are 1.532cm
3/ g.Its small-angle diffraction collection of illustrative plates is seen Figure 16.
Embodiment 12:
The preparation method of large pore volume meso-porous alumina, its concrete technology Step By Condition is as follows:
(1) with the Coaseries kaolin behind the ball milling in 800 ℃ of roastings, then with concentration be 6mol/L HCl solution by solid-to-liquid ratio 1:5.0, in 90 ℃ of stirring and refluxing leaching 3 hours, filter and collect filtrate;
(2) measure the filtrate that 30ml step (1) is collected, add excessive 6.0mol/LNaOH solution, until the Al (OH) that produces
3Precipitation disappears, and is converted into NaAlO fully
2, remove by filter insoluble impurities, collect filtrate for later use;
(3) in the filtrate that step (2) is collected, add 6.0mol/L HCl solution, regulate pH and approach neutrality, make NaAlO
2Be converted into the boehmite precipitation fully, the filtration washing filter cake is collected filter cake as the aluminium source of preparation meso-porous alumina to not containing NaCl;
(4) with filter cake, cetyl trimethylammonium bromide (CTAB) and deionized water by filter cake: cetyl trimethylammonium bromide (CTAB): deionized water is that 1(is with Al in the pickling liquor
3+Content meter): the molar ratio of 0.08:30, mixing and stirring, 40 ℃ of ageings were reacted 48 hours;
(5) filter, 105 ℃ of dry 12h are in 700 ℃ of roasting 6h.
The aperture of the large pore volume meso-porous alumina that this law makes is 10.2nm, and specific surface area is 326.4m
2/ g, pore volume are 1.453cm
3/ g.Its small-angle diffraction collection of illustrative plates is seen Figure 17.
Embodiment 13:
The preparation method of large pore volume meso-porous alumina, its concrete technology Step By Condition is as follows:
(1) with the Coaseries kaolin behind the ball milling in 900 ℃ of roastings, then with concentration be 6mol/L HCl solution by solid-to-liquid ratio 1:4.5, in 90 ℃ of stirring and refluxing leaching 2 hours, filter and collect filtrate;
(2) measure the filtrate that 30ml step (1) is collected, add excessive 6.0mol/LNaOH solution, until the Al (OH) that produces
3Precipitation disappears, and is converted into NaAlO fully
2, remove by filter insoluble impurities, collect filtrate for later use;
(3) in the filtrate that step (2) is collected, add 6.0mol/L HCl solution, regulate pH and approach neutrality, make NaAlO
2Be converted into precipitation fully, the filtration washing filter cake is collected filter cake as the aluminium source of preparation meso-porous alumina to not containing NaCl;
(4) with filter cake, cetyl trimethylammonium bromide (CTAB) and deionized water by filter cake: cetyl trimethylammonium bromide (CTAB): deionized water is that 1(is with Al in the pickling liquor
3+Content meter): the molar ratio of 0.15:50, mixing and stirring changes reactor in 60 ℃ of ageing reactions 72 hours;
(5) filter, 105 ℃ of dry 12h are in 550 ℃ of roasting 6h.
The aperture of the large pore volume meso-porous alumina that this law makes is 9.9nm, and specific surface area is 357.7m
2/ g, pore volume are 1.744cm
3/ g.Its small-angle diffraction collection of illustrative plates is seen Figure 18.
Embodiment 14
The preparation method of large pore volume meso-porous alumina, its concrete technology Step By Condition is as follows:
(1) with the Coaseries kaolin behind the ball milling in 1000 ℃ of roastings, then with concentration be 6mol/L HCl solution by solid-to-liquid ratio 1:5.0, in 50 ℃ of stirring and refluxing leaching 10 hours, filter and collect filtrate;
(2) measure the filtrate that 30ml step (1) is collected, add excessive 6.0mol/L potassium hydroxide solution, until the Al (OH) that produces
3Precipitation disappears, and is converted into KAlO fully
2, remove by filter insoluble impurities, collect filtrate for later use;
(3) in the filtrate that step (2) is collected, add 6.0mol/L HCl solution, regulate pH and approach neutrality, make KAlO
2Be converted into precipitation fully, the filtration washing filter cake is collected filter cake as the aluminium source of preparation meso-porous alumina to not containing KCl;
(4) with filter cake, cetyl trimethylammonium bromide (CTAB) and deionized water by filter cake: cetyl trimethylammonium bromide (CTAB): deionized water is that 1(is with Al in the pickling liquor
3+Content meter): the molar ratio of 0.04:65, mixing and stirring, regulating pH is 3,120 ℃ of ageing reactions 6 hours;
(5) filter, 105 ℃ of dry 12h are in 950 ℃ of roasting 1.5h.
The aperture of the large pore volume meso-porous alumina that this law makes is 10.9nm, and specific surface area is 316.4m
2/ g, pore volume are 1.61cm
3/ g.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the preparation method of a meso-porous alumina may further comprise the steps:
(1) will contain the mineral wealth removal of impurities of aluminum oxide, and aluminium will be converted into meta-aluminate, separate with foreign ion, use acid for adjusting pH, be precipitated, collecting precipitation material and as the aluminium source;
(2) throw out, template and the water that step (1) are obtained are 1:(0.02 ~ 0.5 by molar ratio): mix (20 ~ 70), regulating pH is 3 ~ 10,20 ~ 120 ℃ of ageings at least 6 hours, wherein said template was triton x-100 and/or cetyl trimethylammonium bromide;
(3) with the mixture removal of impurities that obtains after step (2) ageing, obtain solid product, then 450 ~ 950 ℃ of roastings at least 1.5 hours, obtain meso-porous alumina.
2. the method for claim 1 is characterized in that, described step (1) comprising:
The mineral wealth that (11) will contain aluminum oxide are crushed to powder, roasting;
(12) the powder leaching after adopting acid solution to roasting separates liquid phase and solid phase;
(13) in the liquid phase that step (12) obtains, add alkali, remove throw out, obtain meta-aluminate solution;
(14) regulate pH, make the meta-aluminate precipitation, to the throw out removal of impurities, the throw out that obtains is as the aluminium source.
3. method as claimed in claim 2, it is characterized in that the described mineral wealth that contain aluminum oxide are a kind or at least 2 kinds combination in kaolin, nakrite, wilkinite, agalmatolite, montmorillonite, dikite, halloysite, culm clay, clay or the coal gangue;
Preferably, the described powder granularity of step (11) is less than 150 orders, particularly preferably less than 200 orders;
Preferably, the described maturing temperature of step (11) is 450 ~ 1000 ℃, more preferably 470 ~ 950 ℃, is particularly preferably 500 ~ 900 ℃;
Preferably, the described roasting time of step (11) is at least 0.1 hour, more preferably 0.1 ~ 8 hour, more preferably 0.1 ~ 6 hour, is particularly preferably 0.1 ~ 4 hour.
4. such as claim 2 or 3 each described methods, it is characterized in that step (12) is described to be separated into filtration;
Preferably, the described acid of step (12) is a kind or at least 2 kinds combination in hydrochloric acid, sulfuric acid or the nitric acid;
Preferably, the described leaching temperature of step (12) is 50 ~ 150 ℃, more preferably 60 ~ 130 ℃, is particularly preferably 70 ~ 120 ℃;
Preferably, the described leaching time of step (12) is at least 0.5 hour, more preferably 0.8 ~ 10 hour, is particularly preferably 1 ~ 6 hour.
5. such as each described method of claim 2-4, it is characterized in that step (13) is removed throw out by filtering;
Preferably, the described alkali of step (13) is sodium hydroxide and/or potassium hydroxide.
6. such as each described method of claim 2-5, it is characterized in that the described removal of impurities of step (14) is filtration, then washing precipitate;
Preferably, the terminal point of the described adjusting of step (14) pH is 7 ~ 9.
7. such as each described method of claim 1-6, it is characterized in that the described template of step (2) is triton x-100 or cetyl trimethylammonium bromide;
Preferably, the molar ratio of the described throw out of step (2), template and water is 1:(0.04 ~ 0.4): (25 ~ 65) are particularly preferably 1:(0.06 ~ 0.3): (30 ~ 60).
8. such as each described method of claim 1-7, it is characterized in that the described pH of step (2) is 3.5 ~ 9.5, is particularly preferably 4 ~ 9;
Preferably, the described Aging Temperature of step (2) is 25 ~ 110 ℃, is particularly preferably 30 ~ 100 ℃;
Preferably, the described digestion time of step (2) is 8 ~ 90 hours, is particularly preferably 10 ~ 72 hours;
Preferably, the described water of step (2) is deionized water;
Stir when preferably, step (2) is regulated pH.
9. such as each described method of claim 1-8, it is characterized in that the described removal of impurities of step (3) comprises filtration successively, washing, drying;
Preferably, the described maturing temperature of step (3) is 480 ~ 900 ℃, more preferably 500 ~ 800 ℃, is particularly preferably 550 ~ 700 ℃;
Preferably, the described roasting time of step (3) is 1.8 ~ 8 hours, is particularly preferably 2 ~ 6 hours.
10. a meso-porous alumina is characterized in that, described meso-porous alumina is by each described method preparation of claim 1-9.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107199027A (en) * | 2017-05-24 | 2017-09-26 | 天津大学 | Porous alumina cladding titanium dioxide photochemical catalyst and Preparation method and use |
CN110372019A (en) * | 2019-08-15 | 2019-10-25 | 昆山钛研环保科技有限公司 | A kind of preparation method of meso-porous alumina |
CN114054005A (en) * | 2021-11-19 | 2022-02-18 | 昆明理工大学 | Method for preparing mesoporous alumina adsorption material from industrial solid waste aluminum ash |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6214312B1 (en) * | 1998-07-22 | 2001-04-10 | Institut Francais Du Petrole | Process for synthesising aluminas in a basic medium |
CN101492170A (en) * | 2009-02-26 | 2009-07-29 | 同济大学 | Method of manufacturing mesoporous nano- aluminum oxide |
CN101850998A (en) * | 2010-06-18 | 2010-10-06 | 长春市超威新材料科技有限公司 | Method for co-producing aluminum oxide and sodium carbonate from coal gangue |
-
2012
- 2012-11-29 CN CN201210500632.5A patent/CN103011219B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6214312B1 (en) * | 1998-07-22 | 2001-04-10 | Institut Francais Du Petrole | Process for synthesising aluminas in a basic medium |
CN101492170A (en) * | 2009-02-26 | 2009-07-29 | 同济大学 | Method of manufacturing mesoporous nano- aluminum oxide |
CN101850998A (en) * | 2010-06-18 | 2010-10-06 | 长春市超威新材料科技有限公司 | Method for co-producing aluminum oxide and sodium carbonate from coal gangue |
Non-Patent Citations (2)
Title |
---|
Q. LIU ET AL.: "《Synthesis, characterization and catalytic applications of mesoporous γ-alumina from boehmite sol》", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
李传润等: "《介孔氧化铝的研究进展》", 《化学进展》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107199027A (en) * | 2017-05-24 | 2017-09-26 | 天津大学 | Porous alumina cladding titanium dioxide photochemical catalyst and Preparation method and use |
CN110372019A (en) * | 2019-08-15 | 2019-10-25 | 昆山钛研环保科技有限公司 | A kind of preparation method of meso-porous alumina |
CN114054005A (en) * | 2021-11-19 | 2022-02-18 | 昆明理工大学 | Method for preparing mesoporous alumina adsorption material from industrial solid waste aluminum ash |
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