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preparation of nanoscale gamma-alumina

preparation of nanoscale gamma-alumina
preparation of nanoscale gamma-alumina

Chemical Engineering Journal 157 (2010) 67–72

Contents lists available at ScienceDirect

Chemical Engineering

Journal

j o u r n a l h o m e p a g e :w w w.e l s e v i e r.c o m /l o c a t e /c e

j

Azeotropic distillation-assisted preparation of nanoscale gamma-alumina powder from waste oil shale ash

Baichao An,Guijuan Ji,Wenying Wang,Shucai Gan ?,Jijing Xu,Guimei Gao,Guanghuan Li

College of Chemistry,Jilin University,6Ximinzhu street,Changchun 130026,PR China

a r t i c l e i n f o Article history:

Received 1June 2009

Received in revised form 22October 2009Accepted 23October 2009Keywords:Oil shale ash

Azeotropic distillation Nanoscale

Gamma-alumina

a b s t r a c t

A combined process was proposed for the utilization of waste oil shale ash (OSA)in the production of gamma-alumina nanoparticles.The process consisted of two stages,leaching and sintering.The ultrasonic technique followed by a heterogeneous azeotropic distillation process in the presence of polyethy-lene glycol (PEG)was carried to ensure complete elimination of the residual water in the precipitate.The structural and morphological properties of the calcined nanocrystalline powders were character-ized by X-ray diffractometer (XRD),transmission electron microscope (TEM),Brunauer–Emmett–Teller nitrogen-gas adsorption method (BET).The as-prepared precursor hydroxides were analyzed using thermogravimetric–differential thermal analysis (TG–DTA),Fourier transform infrared spectroscopy (FT-IR),and X-ray photoelectron spectroscopy (XPS).The results indicated that the gamma-alumina powder with a uniform particle is well dispersed and the particle size is 20–40nm;the waste OSA can be utilized to produce gamma-alumina nanoparticles.

? 2009 Elsevier B.V. All rights reserved.

1.Introduction

Today,there is a growing interest in developing low-cost energy resource in the world.As a possible alternative,oil shale,which is a natural kerogenous rock,has been used to generate electricity and extract oil for almost a century.A by-product ?y ash from oil shale processing is OSA,which is considered as a serious environmental pollutant [1].Therefore,it is necessary to develop a new approach to OSA management.So far,most research focused on the aspect of building materials [2–7]and adsorbent [8–16].Synthesizes of tobermorite [17]and calcium-alumino-slicate hydrate [18]have been also reported as possible ways for the utilization of OSA.

Nano-sized alumina has extensive potentiality for being used in chemical absorbent,gas sensor,catalysts,and ceramic raw mate-rial.Considerable effort has been put into develop wet chemical synthesis methods because they offer convenient routes for ultra-?ne and high-purity alumina nanopowder.However,the alumina particles were often found to be agglomerated on drying and calci-nation.To solve this problem,various methods for the reduction of the particle size have been reported,including sonochemical synthesis [19,20],azeotropic distillation [21,22],and supercritical-water processing [23]and so on.

In this work,we aim to synthesize gamma-alumina nanopowder using OSA as alumina source via the ultrasonic technique in the

?Corresponding author.Tel.:+8643188502259.E-mail address:gansc@https://www.doczj.com/doc/593685670.html, (S.Gan).

hydrolysis–condensation stage followed by azeotropic distillation.The dispersion mechanism of gamma-alumina nanopowder is also proposed based on the present experimental facts.2.Materials and methods 2.1.Raw materials and reagents

Samples of OSA were collected from the factory in Huadian city of Jilin Province.The organic contents (loss-on-ignition,LOI)and metal contents of oil shale are shown in Table 1.The carbon dioxide gas,with a purity of 99.99%,was purchased from Changchun Xin-guang Gas Manufacturing Co.,Ltd.Other reagents were purchased from Beijing Chemical Reagent Research Institute.All chemical reagents were analytical grade.

2.2.Ultrasonic irradiation facility and parameters

The low powder ultrasonic radiation was performed in an ultra-sonic cleaner (KQ-100DB,Kunshan Inc.,China)that produced a 40kHz ultrasound at its bottom.Bath capacity of the sonicator is 3L.Its power can be changed from 40to 100W.2.3.Experimental procedure

The preparation of the nanoscale alumina from OSA is schemat-ically sketched in the ?owchart of Fig.1and involves two stages.

1385-8947/$–see front matter ? 2009 Elsevier B.V. All rights reserved.doi:10.1016/j.cej.2009.10.048

68 B.An et al./Chemical Engineering Journal157 (2010) 67–72

Table1

Chemical component of oil shale and oil shale ash.

Component%Raw oil shale%Raw oil shale ash

Silicon dioxide31.6863.58

Titanium dioxide0.390.75

Ferric oxide 4.23 5.47

Aluminum oxide10.7716.69

Phosphorous pentoxide0.260.26

Manganese oxide0.050.13

Calcium oxide 1.63 5.12

Magnesium oxide 1.84 2.51

Potassium oxide0.84 1.68

Sodium oxide0.40 1.02

LOI47.85 2.24

2.3.1.Leaching of aluminium

A porcelain boat,containing20g120-mesh OSA and8g sodium chloride was heated at700?C for3h and then air-dried.Subse-quently,the leaching experiments were performed in a1000mL three-necked?ask heated in a hemispherical mantle kept constant within±0.5?C and connected to a mechanical agitator,equipped with twin-bladed impeller and shaft coated by Te?on.For minimiz-ing aqueous loss,a re?ux condenser was applied.After5h,the leach liquor was separated from the residue by vacuum?ltration.Then, 6M sodium hydroxide solution was added to the leaching liquor to adjust the pH to13.After?ltration,the supersaturated sodium aluminate solution was obtained,and the aluminum concentration is shown in Table2.

2.3.2.Synthesis of gamma-alumina nanoparticles

Approximately0.6g surfactant(polyethylene glycol,PEG)was added to the supersaturated sodium aluminate solution.To this solution,carbon dioxide was injected until the pH value of the mixture was9.Under ultrasonic radiation(for30min,60?C),the reaction mixture was further aged about11.5h.The resulting white precipitate was recovered and washed with anhydrous ethanol sev-eral times to obtain the as-synthesized product(marked as S1).Table2

Chemical composition of leaching and puri?ed solution of elements.

Element Leaching

solution of OSA

(?g mL?1)

Puri?ed

solution of OSA

(?g mL?1) Aluminum985.400983.900

Calcium10.170 1.077 Manganese37.1407.435

Iron 1.9420.000 Titanium0.1310.000

Subsequently,S1was transferred into a rockered?ask containing 30mL of n-butanol.After distilling at117?C(the boiling point of n-butanol)for35min,the remaining n-butanol was removed through oven-drying(100?C for12h)to obtain loose powder(marked as S2).This powder was calcined at550?C for2h to obtain nano-sized gamma-alumina powder.

2.4.Characterization

The chemical compositions of the OSA were determined by X-ray?uorescence(XRF)analysis(PW1404/10.Philips,Hol-land).The mineral leachates and their puri?ed solution were analyzed using inductively coupled plasma mass spectrometry (ICP-MS),model X Series II,USA.X-ray diffraction(XRD)anal-ysis for powders was carried out by D/Max-IIIC(Rigaku,Japan) with Cu K?radiation.Powder morphology and dispersity were observed on transmission electron microscope(TEM,JEM-2000EX, Japan).The N2adsorption measurement was examined by a sur-face analyzer(ASAP2010,USA)and the BET

surface area,and

the pore volumes were calculated.The pore size distributions

were estimated by the Barrette–Joynere–Halenda(BJH)method.

Thermogravimetric–differential thermal analysis(TG–DTA)curves

of the samples were recorded on a TG-8120(Rigaku,Japan)using

alpha-alumina as the standard materials.Infrared spectra of the

samples were investigated on a FT-IR(Nicolet Impact410,USA)by Fig.1.Flowchart for the synthesis of gamma-alumina nanoparticle.

B.An et al./Chemical Engineering Journal157 (2010) 67–72

69

Fig.2.XRD pattern of the gamma-alumina nanoparticle.

KBr disk method.The surface of precursor was analyzed by X-ray photoelectron spectroscope(XPS)(Thermo ESCALAB250,UK).

3.Results and discussion

3.1.Characterization

3.1.1.Properties of alumina nanopowder

Representive XRD patterns are shown in Fig.2for the as-made gamma-alumina prepared from OSA.The diffraction patterns of the calcined products show consistent with the standard diffraction data for gamma-alumina(JCPDS Card10-0425).Gamma-alumina, as transition alumina,is disordered crystalline phases formed through the thermal dehydration of aluminum hydroxides and oxy-hydroxides[24].It can be seen that the widths of the peaks are characteristic of a low-crystalline material as expected for such a low calcinations temperature and short time.On the basis of Scher-rer equation,the crystal size of products is calculated from the full width at half-maximum are16nm.

Fig.3shows the transmission electron microscopy of gamma-alumina.The nanoparticles of the product has good dispersity without hard agglomerate and are uniform in size and shape.The average diameter is20–40nm,which is basically in accordance with the XRD results mentioned above.The dispersity of the prod-uct is consistent with the TEM result(calcination temperature, 600?C)reported by Wang et al.[25].

The textural properties of the gamma-alumina powders are further investigated by the N2adsorption–desorption and pore size distribution(PSD)analyses.The result shows that the sample has a speci?c surface area of about191.7m2/g,pore volume of0.445cm3/g,and pore size of9.2nm.The nitrogen adsorption–desorption isotherm are shown in Fig.4.The isotherm obtained for the sample was of type IV which is the characteristic feature of the mesoporous materials[26,27].The desorption cycles of the isotherm showed a hysteresis loop is attributed to the cap-illary condensation occurring in the mesopores[28].The shape of the hysteresis loops is identi?ed with the speci?c pore shape.The adsorption–desorption branches of the sample is almost parallel and vertical over a wide range of p/p0showing the H1type of the hysteresis loop.Such type of hysteresis loop is often associated with cylindrical mesopores open at both ends[29].

Fig.5depicts that the PSD of the products is trimodal with the peak pore diameters at3,16and78nm.This implies that the as-made gamma-alumina consisted of interpenetrating meso-(pores below50nm)and macrostructures(pores above50

nm).

Fig.3.TEM micrograph of the gamma-alumina nanoparticle.

3.1.2.Properties of precursors

The TG and DTA results for the precursor powder(S2)are shown in Fig.6.The TG curve displays two weight-loss stages.The?rst stage at below240?C is associated with the removal of adsorbed water.In this temperature range,the DTA curve show only one endothermic peak at201?C,which is attributed to the desorption of the interlayer water.The second stage located at240–450?C, the corresponding DTA curve show a broad exothermic peak.Spe-cially,the endothermic peak at321?C associated with the phase transformation of transition alumina.

Fig.7shows the FT-IR spectra of precursors S1and S2.The main difference between S1and S2is the adsorption bands at2915 and2847cm?1,which can be attributed to the vibration of–CH2–groups of butanol and PEG[30].And the peak at1377cm?1(S2)

is Fig.4.N2adsorption–desorption isotherm of the gamma-alumina nanoparticle.

70 B.An et al./Chemical Engineering Journal

157 (2010) 67–72

Fig.5.Pore size distribution of the gamma-alumina

nanoparticle.

Fig.6.TG–DTA curves of

precursors.

Fig.7.FT-IR spectra of S x series of

precursors.

Fig.8.XPS spectra of S x series of precursors.

coherent with ?3vibration of CH 3–groups,implying the presence of n-butanol.The adsorption peak at 1633cm ?1(S 1)and 1632cm ?1(S 2)are attributed to the complex peak of the excess water interca-lated in the layers of precursors [31]and –OH groups on the surface of aluminium hydroxide and alcohol [32].The C–O stretching vibra-tion peak of CH 3CH 2O–or CH 3(CH 2)2O–groups at 1070cm ?1(S 1,S 2)can also be monitored.The adsorption at 3433and 3427cm ?1(S 1,S 2)are associated to the hydroxyls on the precursor surface.Fig.8is the XPS spectra of pristine precursor (S 1)and butanol-coated precursor (S 2).For S 1,the O 1s core level spectrum presents peak at binding energy of 531.79±0.10eV,which associates with –OH groups in AlOOH structure.After coating,O 1s peak appears at lower energy of 531.59±0.10eV and its intensity decreases sig-ni?cantly.This is because the presence of O 1s peak from the Al–O–C 4H 9groups.This suggests that some n-butanol molecules are chemisorbed on the surface of the precursors.The result also agrees with the FT-IR analysis.

3.2.Overview of the synthesis process

The chemical compositions of the OSA before and after the leaching process are presented in Table 2.It can be seen,the ther-mal and acid treatments are ef?cient,resulting in a high-purity aluminum solution with very low level of remaining calcium and magnesium.

During the present precipitation process,the distribution of alu-mina nanopowder indicates the particle size of precursor is quite small.Also,the precursor has good chemical reactivity due to the crystal defects result from the ultrasound radiation [33].There-fore,the obtained crystal of aluminum hydroxide is important for nanoceramics and could even be used as seed particles in the Bayer process.Additionally,it should be note that ultrasound can accel-erate the breeding nucleation [34].

3.3.Powder dispersion

Hard agglomeration occurs upon drying and calcinations due to the hydrogen bonds between water molecules and surface –OH groups on particles.In the present investigation,we combine the azeotropic distillation with surface modi?cation and sonication to prevent hard agglomeration.The experiments show that the products as-made are well dispersed,and the possible dispersion mechanism of this combined method can be depicted as follows.

B.An et al./Chemical Engineering Journal157 (2010) 67–7271

PEG is terminated by alcohol groups that render it reactive with respect to the surface hydroxyls of the powder[35]:

Al–OH+HO(CH2CH2O)R→Al–O–(CH2CH2O)x R+H2O

During the present precipitation process,PEG adsorbed on the surface of the formed aluminum hydrate.Therefore,the accessi-bility is decreased due to the spatial effects of PEG molecular.On the other hand,the porous structures of the nanoparticles could be attributed to the combustion of the coated PEG and n-butanol during the calcination.

Ultrasonic radiation is an effective method to prepare nanoscale ultra?ne powder[36–38].It is known that20kHz ultrasonic radi-ation can rupture chemical bonds effectively[39]and so large aggregates are not obtained using this technique.Also,the other two aspects should be noted:(1)during the present precipitation process,PEG can adsorb on the surface of the formed aluminum hydrate.The coated PEG would prevent the hydrogen bonding formed between the neighbouring particles.On the other hand,a quick coagulation of the formed colloids would lead to the forma-tion of loose particles with large particle size,and meantime,large amount of PEG would be enfolded in these loose particles,which would weaken dispersion effect of PEG.Herein,the sonication can destroy the loose particles and then result in the re-adsorption of PEG on the formed particles.(2)n-Butanol was selected in this work because of its highest water content in the azeotrope (44.5wt%)among several practicable water–organic binary sys-tems[40].However,only about10wt%of water is miscible in n-butanol at room temperature.Sonication enhanced the mixing of the hydrous gel and n-butanol,which would bene?t the dehy-dration of the following azeotropic distillation process.

Azeotropic distillation can remove the terminal hydroxyl groups and physically adsorbed water molecules on particle surface via distillation by forming water–organic solvent binary azeotrope. The butoxy could replace the H2O/OH groups of the precipitate with a hydrophobic tail outside.The IR bands in Fig.7can cer-tify the presence of n-butanol in the https://www.doczj.com/doc/593685670.html,rge quantity of adsorbed water is squeezed out due to the compact stacking of organic species on the surface of inorganic precursors[41].This result is con?rmed by the TG–DTA analysis.

4.Conclusions

Nanostructured gamma-alumina powder has been prepared from OSA.Azeotropic distillation combine with ultrasound irra-diation and surfactant modi?cation effectively dehydrate hydrous alumina gel and thus prevent the formation of hard agglomerations. Calcinations product of the gamma-alumina particles exhibited uniform shapes.The approach presented herein might be applied to the production of gamma-alumina nanoscale powder.Further-more,it opens a new way of promising application of OSA. Acknowledgements

This work has been funded by the Scienti?c Research Pro-gram No.:20051015,Development Program of China(863Program, Grant2007AA06Z202)and No.:20070405.

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minum hydrate with poly(ethylene oxide)surfactant,Chem.Mater.14(2002) 2086–2093.

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雅思口语素材

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Useful Expressions: Words and phrases Friends and communication: solidify/ strengthen/ enhance/ promote communication / connection with mutual understanding relationship network/circle of f r i e n d s cultivate/develop friendship with s b . keep steady relationship with sb. establish interpersonal networksac build up the social circle spur message transmission Knowledge and experience widen one’s outlook broaden one’s vision/horizon acquire knowledge and skills comprehensive/overall quality

expand/enlarge one’s scope of knowledge knowledge reserve/base/storage theoretical knowledge practical skills social experience broaden one’s knowledge base promote one’s overall/ comprehensive competence accumulate experiences learn lessons from past experiences Work and experience the scarcity of employment o p p o r t u n i t i lay the foundations for career p r o s p e r i t y

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