CN103787393B

CN103787393B - A kind of preparation method of aluminium oxide

Info

Publication number: CN103787393B
Application number: CN201210427681.0A
Authority: CN
Inventors: 姚运海; 丁莉; 周勇; 郭蓉; 杨成敏
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2012-11-01
Filing date: 2012-11-01
Publication date: 2016-06-22
Anticipated expiration: 2032-11-01
Also published as: CN103787393A

Abstract

The preparation method of a kind of aluminium oxide of disclosure, joins carry out coprecipitation reaction in the aqueous solution containing Polyethylene Glycol by aluminum salt solution and precipitant stream；Precipitate through aging, filter, obtain boehmite dry glue after drying, prepare γ-Al after boehmite dry glue is fired₂O₃Powder body。The method technique is simple, production cost is low, and it is few that the aluminium oxide of preparation has well-regulated layer structure, powder granule is reunited, and greatly, specific surface area is high, and environmental pollution is little, it is easy to accomplish industrialized production for pore volume, aperture。

Description

A kind of preparation method of aluminium oxide

Technical field

The preparation method that the present invention relates to a kind of aluminium oxide, the preparation method relating in particular to a kind of aluminium oxide with layer structure。

Background technology

Alumina material is widely used in the numerous areas such as chemical industry, medical science, electronics, refractory material, environmental protection。Especially aluminium oxide is with a wide range of applications in fields such as catalysis, separation and multifunction device (nano-reactor, optics, bio-separation thin film and chromatograph packing material) manufactures, the pattern of alumina material is had particular/special requirement by these application, it is necessary to synthesizes size uniformity, have the alumina material of certain regular appearance (fiber, tubulose, stratiform, thin slice and spherical)。

CN200910196552.3 discloses a kind of method preparing sheet-shaped alpha-alumina particles by molten-salt growth method。The method prepares Alpha-alumina presoma with technical grade sodium aluminate for raw material, adopts the mixed method of the collosol and gel in molten-salt growth method and ball milling to prepare particle diameter at 2～18 μm, nearly monodispersed sheet-shaped alpha-alumina particles by addition nano-sized crystal α-Al₂O₃Crystal seed and some additives control the pattern of sheet-shaped alpha-alumina particles, have that the purity that technical process is simple, prepare product is higher, low cost and other advantages。

The preparation method that CN200610127935.1 discloses a kind of flake ultrafine aluminium hydroxide, its preparation process is the regulator being added to polyalcohols in sodium aluminate solution, and the sodium aluminate solution containing polyhydric alcohol adds ultra-fine gel aluminum hydroxide decomposition of crystal seed or the sodium aluminate solution selfdecomposition containing polyhydric alcohol；The slurry of reaction through solid-liquor separation, washing, prepare the aluminium hydroxide micro powder of the lamellar of different-grain diameter after drying, by controlling different decomposition technique conditions, the hydroxide flake aluminum micropowder of different-grain diameter can be prepared。

Relative to the preparation method of openly more lamellar, spherical, fibrous alumina, preparation has the aluminium oxide of layer structure and but rarely has report。Preparation method of a kind of Synthesis of Lamellar Mesostructured Alumina by Supramolecular Templating disclosed in " SCI " 20 volume 4 phase 507-510 pages in 1999 such as neat favorable to the people grade; utilize alkyl sodium sulfate at room temperature to synthesize stratiform alumina having mesoporous structure as template, investigate the impact on stratiform aluminium oxide mesopore phase structure parameter of surfactant carbon chain length and surfactant mixed proportion。When using single surfactant as template, the interlamellar spacing d of stratiform alumina having mesoporous structure and the long range order of layer structure thereof increase along with the increase of surfactant carbon chain length；If using C₈H₁₇SO₄Na and C₁₄H₂₉SO₄Na mixed surfactant, as mixed templates, works as C₁₄H₂₉SO₄When Na molar fraction x is in 0～0.5, interlamellar spacing substantially constant, close to situation when having the single surfactant of the two average carbon number (n=11) as template；As x > 0.5 time, interlamellar spacing is gradually increased with the increase of x。The method preparation process is complicated, need use template to cause high expensive。

Summary of the invention

For the deficiencies in the prior art, the preparation method that it is an object of the invention to provide a kind of stratiform aluminium oxide with regular pore structure。The method technique is simple, production cost is low, and the alumina powder jointed particle agglomeration of preparation is few, and greatly, specific surface area is high, and environmental pollution is little, it is easy to accomplish industrialized production for pore volume, aperture。

The preparation method of a kind of aluminium oxide, joins carry out coprecipitation reaction in the aqueous solution containing Polyethylene Glycol by aluminum salt solution and precipitant stream；Precipitate through aging, filter, obtain boehmite dry glue after drying, prepare γ-Al after boehmite dry glue is fired₂O₃Powder body。

Polyethylene Glycol (PEG) described in the inventive method includes one or more mixing in the Polyethylene Glycol of arbitrary molecular weight such as PEG800, PEG2000, PEG4000, PEG6000, PEG8000。In aqueous solution containing Polyethylene Glycol, Polyethylene Glycol is any concentration。

Aluminium salt described in the inventive method and precipitant can be all the raw material of industry。Described aluminium salt includes one or more mixing in aluminum chloride, aluminum sulfate and aluminum nitrate, it is preferable that aluminum sulfate。Aluminium salt concentration 10-80g Al in aluminum salt solution₂O₃·L^-1。Described precipitant is alkaline solution, including one or more mixing in ammonium bicarbonate soln, sodium bicarbonate solution, ammonia spirit, sodium hydroxide solution, potassium hydroxide solution, aqua calcis and sodium aluminate solution。Preferred sodium aluminate solution in all of alkaline solution, sodium aluminate solution concentration is 15-150g Al₂O₃·L^-1。

In the inventive method, coprecipitation reaction process pH value is maintained between 6-9, and temperature controls at 10-60 DEG C。Aging temperature controls at 30-90 DEG C, and pH value is maintained at 6-9, and the time is 0.5-10h。

In the inventive method, boehmite dry glue sintering temperature is 500-700 DEG C, and roasting time is 2-6h。

Compared with prior art, the preparation method of a kind of aluminium oxide of the present invention has the advantage that

(1) the inventive method carries out the co-precipitation reaction of aluminum salt solution and alkaline solution in Aqueous Solutions of Polyethylene Glycol, and prepares the stratiform aluminium oxide with regular pore structure by controlling suitable reaction condition；

(2) precipitate in the inventive method through aging, filter, obtain boehmite dry glue after drying, before and after roasting, alumina grain morphology change is little, and after roasting, the alumina powder jointed particle agglomeration of preparation is few, and pore volume, aperture are big, and specific surface area is high；

(3) the inventive method technique is simple, production cost is low, and environmental pollution is little, it is easy to accomplish industrialized production。

Accompanying drawing explanation

Fig. 1 is the boehmite dry glue crystal grain SEM image of embodiment 1 preparation。

Fig. 2 is the boehmite dry glue crystal grain TEM image of embodiment 1 preparation。

Fig. 3 is the γ-Al of embodiment 1 preparation₂O₃The TEM image of powder body, wherein illustration is γ-Al₂O₃The SAED figure of powder body。

Fig. 4 is the SEM image that comparative example 1 obtains boehmite dry glue。

Detailed description of the invention

Further illustrate process and the effect of the inventive method below in conjunction with embodiment, but following example do not constitute the restriction to the inventive method。

Embodiment 1

Taking technical grade aluminium hydroxide and sodium hydroxide powder, being configured to concentration is 100g Al₂O₃·L^-1Sodium aluminate solution。Taking technical grade sulphuric acid aluminium powder, being configured to concentration is 40g Al₂O₃·L^-1Aluminum sulfate solution。50g polyethylene glycol 6000 is dissolved in 2000ml water, temperature is maintained at 50 DEG C, under stirring, aluminum sulfate solution and sodium aluminate solution stream are joined in polyethylene glycol 6000 solution, the flow-control of aluminum sulfate solution is at 10ml/min, regulate the flow of sodium aluminate solution, make system pH be maintained at about 8。Through, in 90min and after end, raising system temperature to 70 DEG C, ageing 2h。Sucking filtration serosity, filter cake deionized water making beating washing, 100 DEG C dry, obtain boehmite dry glue, and SEM image is shown in Fig. 1, and TEM image is shown in Fig. 2。600 DEG C of roasting 3h, obtain γ-Al₂O₃, TEM image is shown in that Fig. 3, nitrogen absorption under low temperature record γ-Al₂O₃S_BET=279m²/ g, V_P=0.88ml/g, D_P=124.7?。

Embodiment 2

Taking technical grade aluminium hydroxide and sodium hydroxide powder, being configured to concentration is 20g Al₂O₃·L^-1Sodium aluminate solution。Taking technical grade sulphuric acid aluminium powder, being configured to concentration is 80g Al₂O₃·L^-1Aluminum sulfate solution。30g Macrogol 2000 is dissolved in 2000ml water, temperature is maintained at 25 DEG C, joins in Macrogol 2000 solution by aluminum sulfate solution and sodium aluminate solution stream under stirring, and the flow-control of aluminum solutions is at 10ml/min, regulate the flow of sodium aluminate solution, make system pH be maintained at about 7。Through, in 90min and after end, raising system temperature to 40 DEG C, ageing 8h。Sucking filtration serosity, filter cake deionized water making beating washing, 100 DEG C dry, obtain boehmite dry glue。500 DEG C of roasting 6h, obtain γ-Al₂O₃, nitrogen absorption under low temperature records γ-Al₂O₃S_BET=258m²/ g, V_P=0.75ml/g, D_P=116.3?。

Embodiment 3

Taking technical grade aluminium hydroxide and sodium hydroxide powder, being configured to concentration is 150g Al₂O₃·L^-1Sodium aluminate solution。Technical grade sulphuric acid aluminium powder, being configured to concentration is 26g Al₂O₃·L^-1Aluminum sulfate solution。40g Macrogol 4000 is dissolved in 2000ml water, temperature is maintained at 50 DEG C, under stirring, aluminum sulfate solution and sodium aluminate solution stream are joined in Macrogol 4000 solution, the flow-control of aluminum sulfate solution is at 10ml/min, regulate the flow of sodium aluminate solution, make system pH be maintained at about 6。Through, in 90min and after end, raising system temperature to 90 DEG C, ageing 6h。Sucking filtration serosity, filter cake deionized water making beating washing, 100 DEG C dry, obtain boehmite dry glue。700 DEG C of roasting 2h, obtain γ-Al₂O₃, nitrogen absorption under low temperature records γ-Al₂O₃S_BET=301m²/ g, V_P=0.92ml/g, D_P=122.2?。

Comparative example 1

With embodiment 3, simply without Polyethylene Glycol when, carry out co-precipitation。The SEM image obtaining boehmite dry glue is shown in Fig. 4。γ-Al is obtained after roasting₂O₃, nitrogen absorption under low temperature records γ-Al₂O₃S_BET=189m²/ g, V_P=0.32ml/g, D_P=64.6?。

Claims

1. the preparation method of an aluminium oxide, it is characterised in that: aluminum salt solution and precipitant stream are joined and carry out coprecipitation reaction in the aqueous solution containing Polyethylene Glycol；Precipitate through aging, filter, obtain boehmite dry glue after drying, prepare γ-Al after boehmite dry glue is fired₂O₃Powder body, in the described aqueous solution containing Polyethylene Glycol, Polyethylene Glycol is any concentration, aluminium salt concentration 10-80g Al in described aluminum salt solution₂O₃·L^-1, described coprecipitation reaction process pH value is maintained between 6-9, and temperature controls at 10-60 DEG C, and aging temperature controls at 30-90 DEG C, and pH value is maintained at 6-9, and the time is 0.5-10h。

2. method according to claim 1, it is characterised in that: described Polyethylene Glycol includes one or more mixing in PEG800, PEG2000, PEG4000, PEG6000, PEG8000。

3. method according to claim 1, it is characterised in that: described aluminium salt includes one or more mixing in aluminum chloride, aluminum sulfate and aluminum nitrate。

4. method according to claim 1, it is characterised in that: aluminium salt concentration 10-80g Al in described aluminum salt solution₂O₃·L^-1。

5. method according to claim 1, it is characterised in that: described precipitant includes one or more mixing in ammonium bicarbonate soln, sodium bicarbonate solution, ammonia spirit, sodium hydroxide solution, potassium hydroxide solution, aqua calcis and sodium aluminate solution。

6. method according to claim 1, it is characterised in that: precipitant is sodium aluminate solution, and sodium aluminate solution concentration is 15-150g Al₂O₃·L^-1。

7. method according to claim 1, it is characterised in that: boehmite dry glue sintering temperature is 500-700 DEG C, and roasting time is 2-6h。