This invention relates Green synthesis method for preparation of new resin bed by utilizing coconut husk, bagasse, PVA and kaolin for waste water treatment.
BACKGROUND OF THE INVENTION
In this research work agro waste materials have been used in making of useful resin for water treatment like coconut shell or husk and bagasse which is residue after juice extraction from sugarcane. Other material used are Poly vinyl alcohol(PVA/PVP) and chitosan which are biodegradable polymer, these polymer have adhesive nature along with plasticizing property. In addition to these kaolin clay has been used as Filler. These have been used in different proportion ranging 1:1 to 1:3 or 3:1 for coconut Shell waste & bagasse. These agro waste material contain good fibre due to high degree of polymerization of cellulose content. Waste material is dipped in vinegar which is bye-product of sugar industry. Vinegar contains acetic acid which at higher temperature provide softness to the lignin and further with mechanical action lignin becomes softer and provide space for clay and polymer additive (PVA). Fibres are connected with lignin and starch. PVA or chitosan polymers joint the fibrous and provide 3D crosslinked resin bed and which is further converted into nano-size about 40- 100 nm pores through which most of the metal ions present in water are adsorbed in the bed since their size is larger than 100 nm. In this way most of the pollutants get adsorbed and water treatment which clay and First of all waste materials were taken in dried form and then grinded and mixed in different proportions. In this study sol gel or Hummer method have not been used as such but new green synthesis method have been developed for green resin bed.
Method – Method developed for nanocomposite preparation is given below-
This method is also new developed green method as we have not used any harmful solvent or chemical. Limited quantity of vinegar have been reduced. In this process no hazardous or toxic reagent is used. So, the process is environment friendly , so referred as green synthesis method also.
Process in given in 3 steps
a. Drying and Grinding of Agri-waste material( coconut shell or husk and baggase)
b. Pretreatment of agro-waste material with vinegar
c. Preparation of nanocomposite resin with PVA/PVP and clay filler
SUMMARY OF THE INVENTION
In the present invention Agri-waste like coconut Shell or husk and Bagasse have been used in making new composite resin along with plasticizer like PVA or chitosan and Kaolin clay as filler . In this all the materials used are waste materials and no harm full synthetic chemical have been used. For providing adhesive property, PVA and PVP have been used which are biodegradable. This method is green method in which no synthetic chemical has been used and by using such developed resin bed , colour of the effluent or waste water can be reduced along with other water pollutants in terms of BOD, COD , suspended solids, hardness etc.
Selected Agri waste material (coconut husk and bagasse) were dipped in water ( 1:2 to 1;3 ratio) , vinegar ( by product of sugar mill) was added for overnight time. Then these were heated in a closed reactor for about 1-2 hrs and then PVA added (10 to 20%) and material further heated with mixing for 30 mins and kaolin clay ( 10-20%) were added and mixed thoroughly further for 30 mins and then bed was prepared in the form of thin film. Film was dried and utilized.
Such prepared nano-composite was analyzed for adsorption properties. These new material resin has shown good adsorption property for colour, suspended material and dissolved material also. By adsorption colour has been reduced from 70 to 100% and suspended solids reduced from 1800 ppm to 300 ppm and BOD from 400 ppm to 25 ppm and COD from 1600 to 200 ppm.
Resin treatment is given to remove the impurities and various parameters such as BOD, COD, TSS, TDS, PH were determined in lab and metal characterization was done by AAS. The study reveals the application of the treatment on adsorption of contamination and heavy metals from the effluent. It is observed that various polluting parameters are decreased in the range of 90-100 % by using Agro waste nanocomposite resin treatment. By increasing thickness of resin bed, pollutant removal efficiency is enhanced.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure: 1 - SEM image shows composite resin
Figure: 2 - SEM image shows after adsorption of heavy metals by composite
Figure: 3 - FT-IR
Figure: 4 – Resin FT-IR Graph
DETAILED DESCRIPTION OF THE INVENTION
Drying and Grinding of Agro-waste material - Agro-waste bagasse and husk are hammered to convert into small pieces & dried in air with the presence of sun light 4-8 hrs then grinded the waste with the help of grinder for getting powder material.
Pretreatment of agro-waste -
100 gm coconut shell /husk and bagasse 50 gm ( varied the percentage) after drying are taken and dipped in sufficient quality of vinegar ( 20-30 %) solution for 6 to 10 hours then hammering in pestle mortar till get paste.
Further vinegar added in varied quantity from 100ml to 150 ml. it was soaked for overnight after that sample was treated with heat and constant stirring using mechanical stirrer from 60 0C to 900C for 1 to 2 hours till we get pulpy material and then some water was added to wash free lignin and some color of pulp is decolorized.
Preparation of nanocomposite Resin-
Pretreated Agri waste (coconut waste and bagasse) along with fruit peel waste was taken in the 1 liter beaker and 50 -100 ml Vinegar was added and further add 100 ml water with constant stirring and heating at 600C to 900C for different time interval, varied from 45-60minutes. Then some baking soda treatment was given (10 -20%) further it was mixed with strong stirring for 1-2 hours and then washing with water was done. Now brighter pulp was mixed with PVA/PVP as a plasticizer , which was added 10-20% (w/w) of material taken than stirring continues for 10-20 minutes , then Kaolin clay as a filler 5 -15 % w/w of material was added again stirrer for 20-30 min at 400C-500C and left for 30 minutes for development of crosslinked resin bed . After that mixture or sample spread on glass plate for making resin bed in the thickness of 1mm-5mm.Then it is compressed with the help of another glass plate & sufficient weight was kept on second Glass plate. So formed resin bed plate is dried in air with the presence of sunlight. Resin bed is removed from glass plate after 24 hours. Which is tested for adsorption analysis and characterization.
Characterization
Resin bed prepared by above method is characterized by SEM (Call Zeiss Made in Germany Model No. AVO-18) and FT-IR (Nicolet FT-IR of thermos Fischer Company) available in R&D cell of Uttaranchal University.
SEM (Scanning Electron Microscope)
An environmental SEM operating in high-vacuum mode was used for observing the surface morphology of the Coconut shell, waste Nano particle, Before passing through resin and After passing through Resin. Figure 1 shows composite resin and figure-2 shows after adsorption of heavy metals.
FT-IR
The FT-IR spectra of Agro-waste, PVA and Resin Graph were recorded on a spectrophotometer in the range of 400–4000 cm-1 . All of the samples and KBr were previously dried at 1050C in an oven for more than 8 h to remove the moisture. The sample and KBr were mixed together with a ratio of 1:100 (w/w), finely ground and pressed into a disc for the measurement.
The absorption bands are observed in two wave number regions of 3800 - 2750 cm-1 and 1650 - 400 cm-1. The presence of peaks on the spectra of cellulose samples coming from wood pulp corresponds to bands of microcrystalline cellulose (Figure 1), while differences in absorption bands intensities and appearance of new peaks in spectra of recycled cellulosic fibers are observed. Identification of the absorption bands is following. The observed peaks in the wave number range of 3660 - 2900 cm-1 is characteristic for stretching vibration of O-H and C-H bonds in polysaccharides. The broad peak at 3348.1042 cm-1 is characteristic for stretching vibration of the hydroxyl group in polysaccharides. This peak includes also inter- and intra-molecular hydrogen bond vibrations in Agri-waste. The band at 2926.3299 cm-1 is attributed to CH stretching vibration of all hydrocarbon constituent in polysaccharides. Typical bands assigned to Agri-waste were observed in the region of 1650 - 900 cm-1. The peaks located at 1632.55 cm-1 correspond to vibration of water molecules absorbed in Agro-waste. The absorption bands at 1434, 1183, 1027 cm-1 and 896 cm-1 belong to stretching and bending vibrations of -CH2 and -CH, -OH and C-O bonds in cellulose. The absorption bands are observed in two wave number regions of 3800 - 2800 cm-1 and 1650 - 400 cm-1. The band at around 3557.2818 cm-1 has been ascribed to the inner hydroxyls, and the peaks at around the other three characteristic wave numbers are generally attributed to vibrations of the external hydroxyls.
The absorption bands are observed in two wave number regions of 3800 - 2750 cm-1 and 1650 - 500 cm-1. For Resin, The observed peaks in the wave number range of 3650 - 2800 cm-1 is characteristic for stretching vibration of O-H and C-H bonds in polysaccharides. The broad peak at 2847.6972 cm-1 and 2929.0925 cm-1 is characteristic for stretching vibration of the hydroxyl group in polysaccharides. The spectrum shows peaks at 3428.6466 cm-1 for O–H stretching vibration. Peak at 1645.9188cm-1 is assigned for carbonyl –C=O group which is present due to the residual acetate group remaining after the manufacturing of Agro-waste composite resin bed, 1558.1395 cm-1 for C–H bending, 1048.2216 cm-1 for C–H rocking mode and 661.9927 cm-1 for stretching mode of CH2 group of PVA.
Treatment of waste water by using Nano composite resin
Composite bed having 2-3 different layers was prepared and it was further utilized to treat water. Slowly we started pouring the waste water over the prepared composite which help in cleaning the water over the period of 3-4 hours. Similar process was further used to clean waste water (Effluent). overall time taken period was 2 to 3 days. Then we checked various parameters such as BOD, COD, TDS, TSS, pH and hardness values were determined. Treatment of water was given by passing effluent (waste water) through resin bed of h coconut husk, composite of husk with PVA and combined composite.
Table-1 (Pollutant Reduction by coconut husk, bagasse and composite resin )
S.No Parameters Before treatment
(sample) Coconut husk only After treatment
(coconut+ _PVA film ) After treatment
(composite)
5mm After treatment
(10mm resin bad)
1. Colour( Pt-Co) color unit (mg/l) 360 280 120 40 20
2. HardnessPPM 1050 760 520 430 140
3. TSS(PPM) 1080 680 480 320 110
4. COD (PPM) 380 250 200 160 40
5. BOD(PPM) 160 100 80 40 10
From table 1 It is clear when Effluent passes through coconut husk then pollutants are adsorbed from 30 to 35%, while passing through coconut husk and PVA combined film then about 60% reductions are obtained but when when pass through 5mm composite resin bed then about 77-80% reductions are obtained and on further increasing the thickness of resin bed we can decrease the polluting parameters by 90 to 95% significantly.
AAS (Atomic Adsorption Spectrophotometer) Analysis
Analysis of heavy metal by using of AAS (model: Perkin Elmer Atomic Adsorption Spectrophotometer, AA-200)
Table-7 (Heavy metals adsorption with 10 mm resin)
Metals Effluent
Before passing through resin After passing through resin 2 mm
5 mm 10 mm
resin Max reduction%
Chromium

ppb 188 20 10 2 99
Arsenic
ppb 150 12 4 0 100
Lead
ppb 250 40 10 3 99
Nickel
ppb 460 30 12 4 99

When effluent passing through 10 mm resin then heavy metals like Chromium, arsenic, lead and nickel can be adsorbed almost 100% , which is very significant so by using this composite film heavy metals can be removed by adsorption.
When effluent was passed through 1mm resin then adsorption was obtained in the range of 81-85% , further on treatment with Lime and Alum we got about 5 % more removal and which was further increased upto 90-to 95 % removal on passing effluent with 5 mm composite resin. Over all in this work , almost 100% heavy metals can be adsorbed by passing through 10 mm composite resin bed, this composite resin was prepared by using fruit peel waste , agri-waste( coconut husk or shell) , industrial waste ( fly-ash) and PVP( Polyvinyl pyrrolidine) plasticizer. By using this new developed composite, effluent can be treated and color can also be reduced upto siginifcant level, after adsorption of heavy metals and other pollutants, treated water can be utilized by living organism.

We Claim:

1. A Green synthesis method for preparation of new resin bed by utilizing coconut husk, bagasse, PVA and kaolin for waste water treatment comprising the steps of:
Dipping agriwaste material (coconut husk and bagasse) in water (1:2 to 1;3 ratio);
Adding vinegar (by product of sugar mill for overnight time;
Heating in a closed reactor for about 1-2 hrs and then PVA added (10 to 20%) and material further heated with mixing for 30 minutes and kaolin clay (10-20%) are added and mixed thoroughly further for 30 minutes and then bed is prepared in the form of thin film; and Film is dried and utilized;
Wherein Resin treatment is given to remove the impurities.
2. The method as claimed in claim 1, wherein agro-waste bagasse and husk are hammered to convert into small pieces & dried in air with the presence of sun light 4-8 hours then grinded the waste with the help of grinder for getting powder material.
3. The method as claimed in claim 1, wherein 100 gm coconut shell /husk and bagasse 50 gm (varied the percentage) after drying are taken and dipped in sufficient quality of vinegar (20-30 %) solution for 6 to 10 hours then hammering in pestle mortar till get paste.
4. The method as claimed in claim 1, wherein vinegar is added in varied quantity from 100ml to 150 ml; and it is soaked for overnight after that sample was treated with heat and constant stirring using mechanical stirrer from 60 0C to 900C for 1 to 2 hours till gets pulpy material and then some water is added to wash free lignin and some color of pulp is decolorized.
5. The method as claimed in claim 1, wherein Pre-treated Agri waste (coconut waste and bagasse) along with fruit peel waste is taken in the 1 liter beaker and 50 -100 ml Vinegar is added and further add 100 ml water with constant stirring and heating at 600C to 900C for different time interval, varied from 45-60minutes.
6. The method as claimed in claim 1, wherein some baking soda treatment is given (10 -20%) further it is mixed with strong stirring for 1-2 hours and then washing with water was done.
7. The method as claimed in claim 1, wherein brighter pulp is mixed with PVA/PVP as a plasticizer, which is added 10-20% (w/w) of material taken than stirring continues for 10-20 minutes, then Kaolin clay as a filler 5 -15 % w/w of material is added again stirrer for 20-30 min at 400C-500C and left for 30 minutes for development of crosslinked resin bed.
8. The method as claimed in claim 1, wherein after that mixture or sample spread on glass plate for making resin bed in the thickness of 1mm-5mm; then it is compressed with the help of another glass plate & sufficient weight is kept on second Glass plate; so formed resin bed plate is dried in air with the presence of sunlight.
9. The method as claimed in claim 1, wherein resin bed is removed from glass plate after 24 hours; which is tested for adsorption analysis and characterization.