# Patent

## Title
Method of producing an adsorbent from rice hull ash

## Abstract

The invention relates to a method for producing an adsorbent from rice hull ash comprising the following steps of extracting alkali from rice hull for obtaining sodium silicate solution, and mixing the sodium silicate solution with a salt, whereby precipitation of the adsorbent is obtained.

## Background
FIELD OF THE INVENTION
The invention relates to a method for producing an adsorbent from rice hull ash, and in particular for producing magnesium silicate.
BACKGROUND OF THE INVENTION
Adsorptive materials or adsorbents are solids which are able to adsorb considerable amount of gas or liquid, and are widely used in various industrial applications, such as water purifications, bleaching and purifying of fats and oils, drying of air, etc. Being one of the most important adsorbents, synthetic magnesium silicate has gained much attention in the last two decades for regeneration of used frying oil and purification of biodiesel in addition to having been used for column chromatography. Florisil®, Magnesol XL®, and Mizukaife F1® can be counted as being some of the commercially available synthetic magnesium silicates.
Synthetic magnesium silicate (MgO.nSiO2.xH2O) is produced by mixing solutions of sodium silicate and magnesium salts. Sodium silicate is usually prepared by smelting of quartz sand and sodium carbonate at about 1400° C. temperature in ordinary glass-melting furnace. Instead of this high temperature process, a simple low energy chemical method has been proposed to extract amorphous silica from rice hull ash, a co-product of rice industry (Kamath and Proctor, 1998).
Rice hulls or rice husk, a waste co-product of rice industry, contains over 60% silica and are evaluated as raw material for production of a number of silica based products.
When harvested from field, rice kernels are fully enveloped by rice hulls. After being harvested, first stage in milling is removal of hulls. Rice hulls comprise 20-25% of kernel, and mainly contain lignin, cellulose, hemicellulose and silica. Rice hulls are combusted to produce rice hull ash that contains more than 60% silica. Rice hull and rice hull ash have become a source for a number of silicon compounds, including silicon carbide, silicone nitrit, silicone tetrachloride, zeolite, pure silicon, silica, silica gel, sodium silicate.
SUMMARY OF THE INVENTION
The method for producing an adsorbent, namely magnesium silicate, from rice hull ash according to the invention comprises the steps of alkali extraction of silica from rice hull for obtaining sodium silicate solution, and mixing the sodium silicate solution with a magnesium salt, preferably aqueous magnesium sulfate solution whereby precipitation of the adsorbent is obtained.
Alkali solubilization or extraction of silica, according to the present invention, is achieved by means of mixing rice hull ash with a sodium hydroxide solution and boiling the mixture for one hour. After filtering of carbon residue, which is caused by incomplete burning of rice hull, sodium silicate solution is obtained. Various forms of silica and sodium silicate films are obtained from this sodium silicate solution. In the process, according to one preferred embodiment of the invention, magnesium silicate was precipitated from sodium silicate solution by mixing with magnesium sulfate solution.

nSiO2+2NaOH - - - - - Na2O.nSiO2+H2O  (1)

Na2O.nSiO2+mMgSO4- - - - MgO.nSiO2.xH2O+Na2SO4  (2)

The adsorbent obtained from rice hull ash according to present invention can alternatively include calcium silicate (CaO.nSiO2.xH2O). In this case, sodium silicate solution is mixed with a soluble calcium salt, preferably aqueous calcium chloride solution whereby precipitation of the adsorbent is obtained.


PREFERRED EMBODIMENT OF THE INVENTION
A rice hull ash sample was obtained from a rice mill in Thrace, Turkey. The silica content of the sample was 77%, and the surface area was 5.9 m2/g. The first step of the process is alkali extraction from rice hull to obtain sodium silicate solution. For achieving this, 600 mL of 1M NaOH was added to 100 g of rice hull ash in a 1 L flask, covered with a watch-glass, and boiled for one hour with constant stirring using a magnetic stirring bar and a hot plate equipped with a magnetic stirring capacity. The resulting sodium silicate solution was filtered through Whatman #41 ashless filter paper to separate carbon residue, which was subsequently washed with 50 mL of boiling water. The filtrate and washing were combined and allowed to cool to room temperature. The silica content of this solution was found to be 68.2 g/L.
The second step of the process, according to preferred embodiment, is the precipitation of magnesium silicate. 250 mL of the sodium silicate solution was mixed with a magnesium sulfate solution prepared by dissolving 18.7 g of MgSO4.7H2O in 150 mL of water at room temperature. A white precipitate is immediately formed. The precipitate is separated by vacuum filtering from the solution. The precipitate is first washed with distilled water, and then with acetone. The magnesium silicate precipitate was dried at 110° C. for three hours.
The X-ray diffraction patterns of magnesium silicate produced from rice hull and a commercial magnesium silicate sample (Florisil®) were almost identical. The chemical analysis results of the magnesium silicate from rice hull ash are illustrated in Table 1 below.







TABLE 1







Chemical compositions of magnesium silicate produced from rice


hull ash and Florisil ®.










MgO (%)
SiO2 (%)















Magnesium silicate from RHA
12.9
62.8



Florisil ®
15.5
84.0

















TABLE 2







Adsorption capacities and surface areas of magnesium silicate and


Florisil ®










Adsorbed oleic acid
Surface area



(mg OA/g adsorbent)
(m2/g)













Florisil ®
87
181


Magnesium silicate from RHA
100
245









According to Table 1, magnesium silicate showed that it contained 12.9% of magnesium oxide and 62.8% of silicon dioxide. Surface area of magnesium silicate produced was determined as 245 m2/g by the BET method (Table 2). Oleic acid adsorption capacity of the magnesium silicate produced from rice hull ash was determined by adding 0.5 g of the adsorbent to 50 mL of 0.02N oleic acid in hexane and mixing the mixture in a shaker bath for 30 minutes. A control experiment was also conducted using oleic acid solution without adsorbent. The residual oleic acid in solution was determined by alkali titration, and the amount of adsorbed oleic acid was found as 100 mg per gram of the magnesium silicate produced from rice hull ash.
The adsorbent according to present invention can be used optionally for various industrial applications including deacidification and purification of biodiesel, or purification of used frying oil, which is subsequently used for biodiesel production.

## Claims

1. A method for producing an adsorbent from rice hull ash comprising the following steps of extracting alkali from rice hull ash with sodium hydroxide solution for obtaining sodium silicate solution, and mixing the sodium silicate solution with a salt, whereby precipitation of the adsorbent is obtained.

2. The method according to claim 1, wherein the salt is magnesium salt.

3. The method according to claim 2, wherein the magnesium salt is a magnesium sulfate solution.

4. The method according to claim 1, wherein the adsorbent is magnesium silicate.

5. The method according to claim 1, wherein the salt is calcium salt.

6. The method according to claim 5, wherein the calcium salt is a calcium chloride solution.

7. The method according to claim 1, wherein the adsorbent is calcium silicate.

8. The method according to claim 1, wherein the alkali extraction is achieved by means of mixing rice hull ash with a sodium hydroxide solution and boiling the mixture for optionally one hour.

9. The method according to claim 8, wherein carbon residue remaining by incomplete burning of rice hull is filtered.

10. The method according to claim 1, wherein the adsorbent has a minimum capacity of adsorbing oleic acid 100 mg per gram of adsorbent.

11. The method according to claim 1, wherein the adsorbent has a minimum surface area 245 m2 per gram of adsorbent.

12. A method of using an adsorbent according to claim 1, wherein said use optionally comprises deacidification and purification of biodiesel, or purification of used frying oil which is subsequently used for biodiesel production.