Materials Transactions, Vol. 48, No. 12 (2007) pp.

3095 to 3100 Special Issue on Growth of Ecomaterials as a Key to Eco-Society III #2007 The Japan Institute of Metals

Process Parameters Optimization in Preparing High-Purity Amorphous Silica Originated from Rice Husks
Junko Umeda1 , Katsuyoshi Kondoh1 and Yoshisada Michiura2
1 2

Joining and Welding Research Institute, Osaka University, Ibaraki 567-0047, Japan Pipe Division, KURIMOTO LTD, Izumi 559-0023, Japan

Rice husk, one of the main agricultural disposals in Japan, China, India, and South-east Asian countries, is employed as useful renewable resources to produce energy and high-purity silica (SiO2 ), because it consists of 70% organics and about 20% SiO2 . The latter, SiO2 is obtained by burning rice husks in air. The purity of rice husk ashes, however, is reduced by the remains of both carbon contents originated in organics and original metallic impurities such as K, Na, Ca, P, Al, etc. In the previous works, the utilization of the leaching methods by strong acids with a high concentration for both the remove the metallic impurities and the fragmentation of silica structural network was suggested. As their results, the thermal resolution mechanism of organics was discussed by using TGA showing the mass loss behavior during heating. The objective in this study is to clarify the mechanism of the removal of organic components when applying a dilute H2 SO4 leaching treatment with 15% solution concentration. In particular, from a viewpoint of the investigation on molecule structural changes of organics, GCMS (Gas Chromatograph Mass Spectrometer) analysis is carried out on acid-leached rice husks. When using only 1% concentration H2 SO4 solution leaching, a change of cellulose of polysaccharides to levoglucosan via glucose of monosaccharide by hydrolysis and condensation reactions occurred. This reaction accompanied with dehydration always served en endothermic heat, which was found in DTA prole of acid leached rice husk materials. It was also claried that such a low concentration H2 SO4 solution was enough to remove alkali metal elements contained in husks. By optimizing the combustion temperature of rice husks after acid leaching, completely amorphous silica ashes, composing of 99.3% SiO2 and 0.04% carbon, were obtained. [doi:10.2320/matertrans.MK200715] (Received July 30, 2007; Accepted September 7, 2007; Published November 25, 2007) Keywords: rice husk, silica, acid leaching, gas chromatograph mass spectrometer (GCMS) analysis, hydrolysis, dehydration, organics

1.

Introduction

Rice husks are agricultural wastes produced in China, India, and South-east Asia countries, and their annual world production amounts to about 120 million tons.1) The major constituents of rice husks are cellulose, hemi-cellulose, lignin and ash.2) The ash mainly consists of silica (SiO2 ) and some alkali metal impurities. The silicon (Si) atoms exist in the protuberances and hairs on the outer and inner epidermis of the rice husks.3) It indicates that rice husks are available to be employed as useful fuels and resources due to their organics and silica contents. Formation of silica by directly burning husks in suitable equipments installed in the plant is a simple process.4,5) It is considered one of useful recycling processes of agricultural disposals or wastes in the world. At the same time, the pollution problems of husks and their ashes burned in the agriculture eld are reduced. It serves, however, low purity silica materials including remained carbon originated from organics and some metallic oxides coming from original impurities of husks. Extensive researches have been carried out on the purication of SiO2 materials and their applications in using rice husks.68) In particular, the previous works show possibilities to use them widely.9) For example, refractory materials, ceramic or metal matrix composites, semiconductor materials, and additives of cement and concrete are expected.1013) The recent research also reveals a possibility to be employed as reinforcements of magnesium alloys by dispersing Mg2 Si particles via solid-state synthesis.14) From a viewpoint of the utilization of silica particles originated in rice husks, both of purity and crystalline structure should be controlled. In particular, concerning the latter, the crystallization of natural silica easily occurs during heating. That is, to be expected that amorphous silica contained in original rice husks transforms to crystalline

one such as quarts, cristobalite, and trydymite at high temperature.15) IARC (International Agency for Research on Cancer), one part of WHO (World Health Organization), strongly points that the crystalline SiO2 particles belong to Group 1 and have carcinogenic risks to humans in 1997.16) Many researchers had made eorts to purify SiO2 content and reduce impurities such as carbon and metallic oxides. It is reported that alkali metal impurities of K and Na cause the remained carbons in ashes, originated in organics, after burning rice husk. This is because the eutectic reaction between alkali metals and SiO2 element occurs in burning, and the carbon remains in the melt SiO2 .17,18) The acid leaching treatment on rice husks before combustion was useful to obtain high purity silica, and also indicated available analytical methods to evaluate the removal of impurities were introduced by using thermogravimetric analysis and scanning electron microscopy observation on acid-leached rice husks. As results in the previous studies,1923) strong acid leaching treatment can remove the metallic ingredients from husks. In particular, the use of H2 SO4 solutions with 1020% concentration causes charring of the organics (cellulose, hemi-cellulose and lignin) parts which separates out from the silica structural network of rice husks.24) It is also reported that TGA curves of acid-leached rice husks reveal remarkably large mass loss at 503643 K due to a thermal degradation of the above organic components.25) The reason was considered that a strong acid digestion was eective to break down rice husks into small fragments thus exposing more organic components. That is, their pyrolysis can be accelerated more rapidly due to the increase of their exposed surface areas. In the previous experimental data by using TGA proles, it is mainly discussed that the acid leaching treatment is eective for the physical removal and thermal resolution of organics by

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J. Umeda, K. Kondoh and Y. Michiura

pyrolysis and their separation from silica networks. Another paper reported that the hydrolysis of pulps via HCl leaching process was investigated by level-o degree of polymerization (LODP). It is useful for a quantitative evaluation on the progress of hydrolysis, but can not clarify its mechanism by acid leaching treatment. In other words, there are very few discussions on the eects of acid leaching on the molecule structural changes of organics by chemically thermal resolution. Furthermore, thick strong acid solutions with 520% concentration, which are harmful to the environment, are mostly used in the previous experiments. They would also cause more expensive leaching treatments in mass production. The objective in this study is to investigate a molecule structural change of organics contained in rice husks by a dilute H2 SO4 solution leaching in order to establish the environmentally benign process of high purity silica ashes. From a viewpoint of the evaluation on changes in the molecule structures of cellulose, not only conventional analytical approach by TG-TDA and SEM observation, but GCMS analysis on rice husk materials is taken place to quantitatively investigate the eect of acid solution concentration on the chemical reaction of organics. In particular, the relationship between DTA proles accompanied with an endothermic heat and GCMS results showing hydrolysis and dehydration reactions is discussed. At the same time, the content of remained impurities and crystalline structures of their ashes after combustion under dierent temperature is also evaluated by XRF, ICP and XRD analysis, to prepare amorphous silica ashes with high-purity. 2. Experimental Pricedure

Heating ratio; 10 /min.

DTA (a.u)

Sodium Hydrogen Carbonate

Pure water As-received Sulfuric acid

200

400

600

800

1000

Temperature, T /
Fig. 1 DTA proles of as-received rice husk and leached by solution with dierent pH.

ashes, XRD (X-ray Diraction) analysis (Shimazu XRD6100) on acid-leached rice husks burned at various temperatures is carried out. 3. Results and Discussion

Rice husks, harvested in Niigata, Japan are employed as raw materials, and 20 g of them is leached for 15 min. in 500 ml of strong acid (H2 SO4 ) solution; the concentration is 15%, and soaking temperature is kept at 317 K. When using 1020% concentration of thick H2 SO4 solutions in the leaching treatment, it was claried that the charring of organics remarkably occurred, and the color of husks was completely black, corresponding to the previous study.24) The ashes after combustion in air contain a lot of sulfur elements of 0.380.75 mass% originated in acid solution. Therefore, a dilute H2 SO4 solution with such a low concentration is employed. The rinsing treatment on acid-leached husks carried out in water bath to remove the acid from them. After rinsing, they are dried at 373 K for 1hour in mue type furnace. The burning process of dried husks is taken place at 873 K and 1273 K to completely remove organics of cellulose, hemi-cellulose and lignin. The eect of acid leaching treatment on the hydrolysis of organics is evaluated by the exothermic or endothermic heat of each acid-leached rice husks in DTA (Dierential Thermal Analysis) prole analyzed by Shimazu DTG-60. It is measured from 293 K to 1273 K with a heating ratio of 10 K/min. GCMS (Gas Chromatograph Mass Spectrometer, Agilent-5973N) is useful to analyze the hydrolysis of each organic in heating at 673 K. Quantitative analysis of SiO2 , carbon and other elements included in rice husk ashes is taken place by XRF (X-ray uorescence) and ICP (Inductively Coupled Plasma) analysis. To clarify the crystallization temperature of silica of

To evaluate the eect of leaching on hydrolysis of organics contained in rice husks, DTA was carried out on husks washed in solutions with dierent pH (power of hydrogen) value; Sodium hydrogen carbonate (pH 8:1), pure water (pH 7), and sulfuric acid (pH 3:8) were employed. As shown in Fig. 1, when using as-received husks and those via leaching by solutions with pH of 7 and more, the double peaks of exothermic are obviously detected. The previous study reports that the rst peak at lower temperature corresponds to degradation of hemi-cellulose and lignin components, and that at higher temperature is due to the thermal degradation of cellulose which has higher molecular mass than the above organics.25) When using the sodium hydrogen carbonates leaching treatment on rice husks, DTA prole shows no dierence with that in using as-received husks, that is, no available eect of this leaching on the removal or resolution of organics. On the other hand, DTA curve of rice husks via the sulfuric acid leaching treatment reveals a large mount of endothermic heat at 543623 K, and a large mass reduction is detected. Figure 2 shows DTA proles of rice husks leached by hot water (a) and H2 SO4 solution with 2% (b) and 5% (c) concentration at 317 K for 900 s. Figure 3 indicates the dependence of an endothermic heat on H2 SO4 concentration used in the leaching treatment. As shown in Fig. 2(a), when using hot water leaching, a small endothermic heat is detected at 574620 K. Rice husks leached by H2 SO4 solution, shown in (b) and (c), also reveal the endothermic at the same temperature. Furthermore, as shown in Fig. 3, only 1% H2 SO4 solution leaching treatment causes a signicant increase of the endothermic heat, compared to hot water washed specimens. Its value gradually increases with increase in H2 SO4 concentration, and saturates when the concentration is over 3%. According to the previous researches by using 1020% concentration acid solu-

Process Parameters Optimization in Preparing High-Purity Amorphous Silica Originated from Rice Husks

3097

150 100 50

150

(a)

100 50

(b)

V DTA /

0 -50 -100 -150 -200 -250 200 400 600 800 1000 1200

0 -50 -100 -150 -200 -250 200 400 600 800 1000 1200

DTA /

Temperature, T / K
100

Temperature, T / K

(c)
50 0

V
-50

DTA /

-100 -150 -200 -250 200 400 600 800 1000 1200

Temperature, T / K
Fig. 2 DTA proles of raw rice husks (a), and as-acid leached ones by H2 SO4 solution of 2% (b) and 5% (c).

9 8

7 6 5 4 3 2 1 0 0 1 2 3 4 5

H2SO4 concentration (%)

Fig. 3 Dependence of endothermic heat in DTA proles of rice husks on concentration of H2 SO4 solution used in leaching treatment.

tions,24,25) the endothermic accompanied with a remarkably large mass loss corresponds to the pyrolysis of cellulose components in rice husks during combustion. This is due to the increase of exposed areas of organics caused by the small rice husk fragments broken down by strong acid leaching. In

the present study, however, no morphology change of rice husks after the acid leaching by H2 SO4 solution with 5% concentration is shown in SEM observation result in Fig. 4. The appearance of acid washed rice husks is similar to the cone type surface with scale structures, and almost same as as-received raw materials. A few additives on the surface of husks are removed by 5% H2 SO4 leaching. However, a fragmentation of husks into small pieces after acid leaching, as mentioned in the previous work,26) is not observed, that is, the exposed surface areas do not increase signicantly. Accordingly, it is concluded that the organics resolution mechanism of rice husks leached by a low concentration H2 SO4 solution is quite dierent from that in using a higher concentration acid leaching process causing the fragmentation of husks as mentioned above. GCMS analysis on rice husks after H2 SO4 leaching treatment with 1% and 5% concentration was carried out at 673 K for 900 s, compared to raw materials without any leaching. The pre-treating temperature of each specimen is decided as 673 K, because a large endothermic is detected at the same temperature range of DTA prole in Fig. 2. Figure 5 reveals GCMS results on each rice husk, where (a) and (d) are via the acid leaching by H2 SO4 solution 5% and 1% concentration, respectively, and (c) is as-received raw materials without any leaching. The n value of each gure corresponds to the total intensity of detected ions spectra in GCMS analysis. As shown in (a) and (b), there is

Endothermic / kJ.g -1

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J. Umeda, K. Kondoh and Y. Michiura

(a) As-received husk

(b) 5% H2SO4 leached

Fig. 4

SEM observation on surface of as-received rice husk (a) and 5% H2 SO4 leached one (b).

no signicant dierence of them, and both reveal a remarkably large peak at retention time of 7.5 min. Spectrum analysis indicates the peak is due to the occurrence of levoglucosan composed of glucose units. It is also detected in the rice husks after the other acids leaching treatment by HCl or HNO3 solutions in our present study. On the other hand, such a spectrum peak is, however, not observed in using raw materials as shown in Fig. 5(c). In comparing spectra of these materials, they are not signicantly dierent except for the above peak corresponding to levoglucosan components, and each n value is almost same. It means that H2 SO4 leaching treatment causes the chemically structural change of cellulose to levoglucosan only, and has no eect on the other reactions of any components contained in each rice husk. Figure 6 illustrates the molecule structure change of cellulose to levoglucosan units via the hydrolysis and dehydration reaction. By soaking rice husk into H2 SO4 solution, the hydrolysis reaction occurs, and cellulose, (C6 H10 O5 )n is accompanied with H2 O to form a monosaccharide of glucose, C6 H12 O6 with hydroxy groups.27) That is, the polysaccharide of cellulose, not possessing considerable bonding property, has an easy cleavage of a chemical entity into two parts of the monosaccharide by the action of water. During heating at elevated temperature, the dehydration, which is one of condensation reactions, is easily taken place via a reaction between OH and H, and levoglucosan is formed. Therefore, the formation of levoglucosan is accompanied with an endothermic heat due to its dehydration reaction. In compar-

ing the spectrum quantity of levoglucosan peak shown in Fig. 5(a) and (b), that in 5% concentration H2 SO4 leaching is a little larger than that in 1% solution. It means 5% acid solution is more eective to accelerate the hydrolysis of cellulose, and corresponds to the dierence in the endothermic heat of them in Fig. 3. Accordingly, the comparison of this endothermic heat is available to quantitatively evaluate the eect of the acid leaching conditions on the hydrolysis of organics in rice husks. It is also useful to optimize the leaching parameters such as concentration and temperature of acid solutions. On the other hand, as previous studies pointed, the metallic impurities, in particular alkali metal elements of K and Na, contained in rice husks react with silica, so that the crystallization of silica occurs after combustion of rice husks.17,18,20) Therefore, the removal of these impurities by acid leaching is necessary to maintain amorphous structures of silica ashes. They have already claried the eect of high concentration of strong acid leaching on their removal, for example 515% of HCl, HNO3 , and H2 SO4 solutions. In this study, the relationship between the impurity contents and concentration of dilute H2 SO4 solution is investigated in detail. Since the main impurity of raw husks is Ca, the content of Ca and alkali metal of K and Na is quantitatively analyzed by XRF analysis in using ashes after burning each acid-leached husk at 1073 K for 1.8 ks in air. As shown in Fig. 7, Na content gradually decreases with increase in the acid concentration. That of K and Ca is, however, drastically

Process Parameters Optimization in Preparing High-Purity Amorphous Silica Originated from Rice Husks

3099

(*107)

1.2

Abundance / a.u

4 3 2 1 0 0

(a)

n=4.8*1010

K2 O CaO Na2O

Content (mass %)

0.8 0.6 0.4 0.2 0

5 10 Retention time, t / min.

7

15

(*10 )

Abundance / a.u

4 3 2 1 0 0
(*107)

(b)

n=4.9*1010

H2SO4 concentration (%)

5 10 Retention time, t / min. (c)

n=5.0*1010

15

Fig. 7 Dependence of metallic oxide impurities content on H2 SO4 solution concentration.

Abundance / a.u

4 3 2 1 0 0 5 10 Retention time, t / min. 15

Fig. 5 GCMS results on rice husk after H2 SO4 leaching of 5% (a), 1% (b), and as-received one (b).

Accordingly, very dilute H2 SO4 solution is eective to accelerate not only the hydrolysis of organics, but also the removal of metallic impurities of rice husks to purify silica ash. From a viewpoint of a safety in handling silica particles, the optimization of burning temperature of rice husks is necessary to hinder their crystallization and prepare highpurity silica ashes with amorphous structures. The crystalline structure of SiO2 originated in rice husks depends on the thermal history in burning them. Figure 8 shows XRD proles of rice husk ashes after burned at dierent temperature in air, when employing (a) rice husks via 5% H2 SO4 leaching and (b) as-received ones. The former consists of SiO2 with completely amorphous structures, not any crystalline ones, in burning at 1273 K or less. In the case of using asreceived raw materials, the crystallization transformation to cristobalite, shown by c-SiO2 in Fig. 8(b), occurs by 1273 K combustion, and both of amorphous and crystalline structures silica ashes are obtained. This is because of the removal of alkali metals as mentioned in Fig. 7, which hinders a eutectic reaction with silica to cause its liquid phase. This result corresponds well to those in the previous reports,2830) showing that crystallization of silica to cristobalite or tridymite when burning over 1127 K. 4. Conclusions

Fig. 6 Molecule structural changes from cellulose to levoglucosan via hydrolysis and dehydration reactions in employing acid leached rice husks.

reduced by only 1% acid leaching, and after that, it also gradually decreases. XRF and ICP results also indicate that SiO2 purity and carbon content of ashes is 99.3% and 0.04%, respectively when using 5% H2 SO4 leaching treatment.

The recycling process of rice husk, which is one of major agricultural disposals, to produce high purity amorphous silica has been developed. In using the acid leaching by dilute H2 SO4 solution of 15% concentration, GCMS results indicate that the endothermic heat at about 600 K in DTA prole is due to a molecule structural changes from cellulose to levoglucosan via glucose by hydrolysis and dehydration reactions, not morphology changes of rice husks accompanied with small fragments by high concentration acid resolution as mentioned in previous studies. The low concentration less than 3% is also enough to remove metallic impurities of rice husks, in particular alkali metal elements,

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J. Umeda, K. Kondoh and Y. Michiura

(a)

(b)

Intensity (a.u.)

1273K

Intensity (a.u.)

c-SiO2
1273K 873K Before burning

873K

Before burning 20 30 40 50 60 20 30 40

50

60

Diffraction Angle 2

Diffraction Angle 2

Fig. 8 XRD results on ashes after burning at dierent temperature; 5% H2 SO4 leached rice husks (a) and as-received ones without any leaching (b).

for the purication of silica ash. As a result of their removal, the crystallization temperature of original amorphous silica increases, and the formation of cristobalites after burning rice husks at 1273 K is hindered. High purity silica ashes with 99.3% and more are obtained when employing a dilute acid leaching and high temperature combustion. Acknowledgements This project is supported by Research & Technology Development on Waste Management Research Grant, Ministry of the Environment. Authors also thank to Mr. H. Oginuma, a research assistant of JWRI, for his helps in experiments.

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