Presentation On Removal Of Silica From Wheat Straw And Sacchrum Munja

Project GuideMr. A.S.K. Sinha AP, Chemical Deptt. S.L.I.E.T, Longowal

Presented ByJyoti Blehria Gct/095730 Ashok S. Mahara Gct/095701 Khim S. Tangania Gct/095711 Harendra Ku. Singh Gct/095742

CONTENTS
Introduction of sacchrum munja and wheat straw S. munja and wheat straw as raw material for paper industry Problems associated with silica in raw material Chemical analysis of sample without impregnation Impregnation of sample with NaOH and urea Comparison of silica content of sample for different conditions. Conclusions References

SACCHARUM MUNJA
Saccharum munja, known as munja is a grass found in arid areas and along river banks in India. It grows up to 2 meters in height.

It is used as a raw material for thatching roofs, making baskets, as animal feed & it is also used for making ropes. Additional uses like paper making, chemical extraction and carbon production are also considered.

Sacchrum-munja

AGRICULTURAL WASTE-WHEAT STRAW

The global agricultural sector produces billions of tonnes of wheat straw. Only a small fraction of this is used as animal feeds and for energy production. Most of the agricultural wastes are left unused, creating environmental problems due to improper waste management such as on-site burning and landdumping.

on-site burning

WHEAT STRAW AND SACCHRUM MUNJA AS RAW MATERIAL FOR PAPER INDUSTRY:Paper made from wheat straw and munja by mixing with conventional pulp are indistinguishable from regular wood-pulp paper. As a renewable resource they can be replaced annually, compared to much longer growth cycle of wood.

As a source of paper fiber, these takes pressure off the forests.

pulp sources, like wheat straw and munja, are less energy, water, and chemical-intensive. There are some technical challenges, one of which is the issue of silica content, higher in agricultural sources than wood pulp.

Wheat straw

Sacchrum munja

Non-wood pulp production represents less than 10% of total worlds pulp source

PROBLEMS ASSOCIATED WITH SILICA IN THESE RAW MATERIAL: In the recovery furnaces it tends to form glass . which makes it very, very difficult to recover the cooking chemicals.
The reduction in heat transfer efficiencies. If the black liquor is concentrated in a multipleeffect evaporation system, some of the silica precipitates and deposits onto the evaporator heating surfaces, rapidly decreasing their capacity.

Cont.
The presence of silica in black liquor can also cause high black liquor viscosity, which limits the solids concentration that can be achieved during evaporation. As a result, many mills do not concentrate and burn the liquor. They simply discharge it. The presence of silica in the green liquor causes "settling" problems within the causticizing plant.

Scale formed due to silica

PROCEDURE TO DETERMINE SILICA CONTENT IN A SAMPLE:First of all take the known wt. of sample in a crucible. Dry the sample in oven and get the moisture content. Put the sample in muffle furnace for two hours at about 600C, what we get is the total ash content. Cool the ash and add 5ml HCl then evaporate HCl on steam bath (any temp.), this procedure is repeated three times. Finally dilute the mass and heat.

Cont.
Filter on ashless filter paper, then wash the residue with hot water till free from chlorides Dry the filter paper with residue and ignite in furnace at 575C. Cool the ash and take the wt., the wt. obtained is the silica content of the sample.

Silica % = (wt. of silica in gram/wt. of test specimen in gram)

Silica content of different materials-:

Followings data are obtained from literature reviewWheat straw contains 3-10% silica Rice straw contains 9-14% silica Cereals(barley, oat & rye) straw have 1-6% silica Wood on the other hand have less than 1% silica

Methods to solve silica problemBlack liquor desilication with CO2. Two stage causticizing desilication method. Green liquor desilication with lime. And the use of ammonium or potassium based pulping with the liquor disposed as a fertilizer. The appropriate pretreatment (dry cleaning) of straw is one of the solutions to minimize scaling problem in the recovery system. The dry cleaning system is fairly simple; it has low specific power consumption and its investment costs are rather low.

Chemical analysis without impregnation-:

Before carrying out impregnation and desilication experiment, chemical analysis of Wheat straw and sacchrum munja was performed. The results of the analysis are listed bellow-:

analysis wt. of sample moisture % total ash % silica %

wheat straw 10g 14% 5.30% 3.50%

sacchrum munja 10g 22% 4.10% 1.50%

Impregnation of sample :
Impregnation of wheat straw & munja was conducted in a 500 ml beaker, with a provision of heating & liquor circulation. The experimental conditions were maintained as follows-: 10 g of dried sample were soaked with 200g of solution of urea & sodium hydroxide of different concentration, the time of impregnation was also varied.

Experimental condition for straw impregnation-:

temp. (C) 50 50 chemical charge NaOH (%) urea(%) 2 2 5 5 2 2 5 5 10 10

sample sacchrum munja wheat straw

reaction time(hrs) 0.25 0.5 0.75 1 0.25 0.5 0.75 1 15 15

Cont.
After the impregnated samples were air dried, the total ash & acid insoluble ash (silica) were determined.
3.5

comparision in silica content for 2% conc. soln.

3

2.5

silica (%)

2% urea treated w.s.

1.5

1.4

1 1

0.5

2% NaOH treated s.m.

2%NaOH treated w.s.

0.9

2% urea treated s.m.

3 4

0 1 2

3.5 3 2.6 2.5 2 silica (%) 1.5 1 0.5 0 1 1.4 5% NaOH treated (munja) 1
5% urea treated (munja) 5% NaOH Treated (w. straw)

3.2

5% urea treated (w. straw)

Comparison in silica content of wheat straw & munja when treated with 5% NaOH & urea, at 50C for 15 min.

4 3.5 3 Silica % 2.5 2 1.5 s.m. w.s.

1
0.5 0

untreated 2% NaOH

2% urea

5%NaOH

5%urea

Comparison of silica content of sample after impregnation with diff. conc. Soln.

Change in silica content with increase in impregnation time for urea treated
5 4.5 4 3.5

Silica (%)

3
2.5 2 1.5 1 0.5 0 0 min 15 min 30 min 45 min 60 min

w.s. s.m.

Time (min)

Definition of lignin-:
Lignin is called the incrusting material forming a part of the cell wall and middle lamella in wood. It is an aromatic, amorphous substance containing phenolic methoxyl, hydroxyl, and other constituent groups; its chemical structure has not been fully elucidated. In this method of determination, lignin (also known as klason lignin) is defined as constituent insoluble in 72% sulfuric acid.

Acid-insoluble lignin determination-:

Summary of method
The carbohydrates in wood and pulp are hydrolyzed and solublized by sulfuric acid; the acid-insoluble lignin is filtered off, dried and weighed.

Significance-:
Different

raw material such as wood, wheat straw, rice straw, sachhrum-munja etc. contains different amount of lignin. Removal of lignin is a main objective of pulping and bleaching processes.
Determination of lignin content provides information for evaluation and application of processes.

Hardness, bleachability, and other pulp properties, such as color, are also associated with the lignin content.

Experimental procedure to determine lignin content-:

Add 15 ml 72% sulfuric acid to the beakers containing the test specimens (10 to 15C). After the specimen is dispersed, cover the beaker with a watch glass and keep it in a bath at 20 1C for 2 h. Stir the material frequently during this time to ensure complete solution. Add about 300 to 400 mL of water to a flask and transfer the material from the beaker to the flask. Rinse and dilute with water to 3% concentration of sulfuric acid, to a total volume of 575 ml. Boil the solution for 4 h, maintaining constant volume by frequent addition of hot water.

Cont.
Allow the insoluble material (lignin) to settle. If the lignin is finely dispersed, it may require a longer period to settle. Without stirring up the precipitate, decant the supernatant solution.

Wash the lignin free of acid with hot water.

Dry the crucible with lignin in an oven at 105 3C to constant weight. Cool in a descicator and weigh.

Calculation
For each determination, calculate the lignin content in the test specimen as follows: Lignin, % = A 100 / W where: A = weight of lignin, g . W = oven-dry weight of test specimen, g

Procedure for estimation of holocellulose in raw material-:

20g of sample is extracted with a mixture of methanol-benzene (1:2) in a soxholet apparatus. 5g of OD extracted sample is put in 250ml flask and 150ml solution containing 1.5g of Sodium chlorite and 10 drops of acetic acid at 70 C is added to it. The flask is loosely covered and regulated at 70C

After 1hr add another 10 drops of acetic acid and a solution containing 1.5 g of sodium chlorite. This operation is repeated three times every hour. The contents of the flask are cooled in a water bath and filtered immediately. It is finally washed with 50ml acetone and dried under vacuum till constant weight is obtained.

calculation:% moisture in sample = [(initial wt wt of OD sample)/ wt of OD sample] * 100

Holocellulose % = (wt of OD holocellulose/wt OD sample)* 100

% composition of wheat straw without treated

4.8% 1.8%

holocellulose
klason lignin

20.5%

72.9%

Variation in klason lignin & holocellulose content

80 70 72.9 71.4

60
50 (%) composition 40 30 20 10 0 wheat straw without wheat straw treated treated with 2%urea klason lignin holocellulose 20.5 15.4

Urea can be better choice because-:

Urea is easy to handle and to use with no health risks. It can be purchased everywhere and it is considerably cheaper than both NaOH and NH3. For sacchrum munja 2% urea gives best results.

For wheat straw silica content decreases with increase in impregnation time in urea solution.
There is no appreciable change in hollocellulose content & lignin content decreases almost 5% when treated with 2% urea.

CONCLUSIONS-:
Up to 40% silica was removed from sacchrum munja when it was treated with 2% urea. Up to 62% silica was removed from wheat straw when treated with 2% NaOH solution, impregnated for 15 min.

Even low level of chemical charge causes leaching of silica significantly

When impregnation time is increased for wheat straw in urea solution then silica content decreases with time. Urea can be beneficial in removing silica from wheat straw & sacchrum munja.

REFERENCES:
http://www.springerlink.com http://www.sciencedirect.com http://en.wikipedia.org http://www.google.co.in http://www.ineeltechnologies.com/ Pekarovic j., Joyee T.W.: desilication of agricultural residue