FIELD OF INVENTION

The present invention relates to the field of Nanoscience and technology particularly to the design of nanosolution for effluent treatment with all metal nanoparticles either individually or in combination depending upon the nature of effluent.

The present invention is related to new chemical moieties, and more specifically it is
related to novel nanosolution with silver ,gold, Iron, Copper, Nickel etc metal nanoparticles for any effluent treatment.

BACKGROUND OF THE INVENTION

Dyeing industry effluents are one of the most problematic wastewaters to be treated not only for their high chemical oxygen demand, but also for high biological oxygen demand, suspended solids, turbidity, toxic constituents but also for color, which is the first contaminant discernible by the human eye. Dyes may affect the photosynthetic activity in aquatic life due to reduced light penetration and may also be toxic to some aquatic life due to the presence of aromatics, metals, etc. in them (Clarke and Anliker 1980; Zollinger 1987; Mishra and Tripathy 1993; Banat et a/1996; Fu and Viraraghvan 2001; Robinson et a/2001). Dyes have generated much concern regarding its use, due to its toxic effects. It has been reported to cause carcinogenesis, mutagenesis, chromosomal fractures, teratogenecity arid respiratory toxicity. McGeorge et al. (1985) reported the mutagenic activity of textile wastewater effluents, using the salmonella/microsome assay and contributed the highest percentage (67%) of mutagenic effluents. Costan et al. (1993) found that a textile effluent ranked second in toxicity, among eight industrial sectors represented, by using a series of bioassays assessing the acute, sublethal and chronic toxicity at various trophic levels. Sub - chronic exposure (13 week) to benzidine - based dyes resulted in hepatocellular carcinomas and hepatic neoplastic nodules in rats (National Cancer Institute 1978) and carcinomas in very short duration (National Institute for Occupational Safety, 1980). Histopathological changes in the testes of textile wastewater exposed rats (sub - chronic) included a reduction in the number of germ and Leydig cells, resulting in impaired spermatogenesis (Mathur, et al. 2003).

Textile industries consume substantial volumes of water and chemicals associated with dyeing process. Most of the textile dyes are recalcitrant; thereby create problems in the biological treatment of the textile effluents The removal of color from textile effluents has targeted attention over the last few years, not only because of its toxicity, but mainly due to its visibility. Conventional treatment facilities are often unable to remove certain forms of color, particularly those arising from reactive dyes as a result of their high solubility and low biodegradability

The technologies for the removal of pollutants from effluents can be divided into three categories: biological, chemical and physical (Robinson et al., 2001). All of them have advantages and drawbacks. Due to the high cost and disposal problems, many of these conventional methods for treating dye wastewater have not been widely applied at large scale in the textile and paper industries.

Presently, there is no single process capable of adequate treatment, mainly due to the complex nature of the effluents. In practice, a combination of different processes is often used to achieve the desired water quality in the most economical way. A literature survey shows that research has been and continues to be conducted in the areas of combined adsorption-biological treatments in order to improve the biodegradation of dyestuffs and minimize the sludge production.

Biological treatments

Biological treatment is often the most economical alternative when compared with other physical and chemical processes. Biodegradation methods such as fungal decolorization, microbial degradation, adsorption by (living or dead) microbial biomass and bioremediation systems are commonly applied to the treatment of industrial effluents because many microorganisms such as bacteria, yeasts, algae and fungi are able to accumulate and degrade different pollutants ( Fu and Viraraghavan, 2001a and Banat et al., 1996). However, their application is often restricted because of technical constraints.

Chemical methods

Chemical methods include coagulation or flocculation combined with flotation and filtration, precipitation-flocculation with Fe(II)/Ca(OH)2, electroflotation, electrokinetic coagulation, conventional oxidation methods by oxidizing agents (ozone), irradiation or electrochemical processes. These chemical techniques are often expensive, and although the dyes are removed, accumulation of concentrated sludge creates a disposal problem.

There is also the possibility that a secondary pollution problem because of excessive chemical use. Recently, other emerging techniques, known as advanced oxidation processes, which are based on the generation of very powerful oxidizing agents such as hydroxyl radicals, have been applied with success for pollutant degradation. Although these methods are efficient for the treatment of waters contaminated with pollutants, they are very costly and commercially unattractive. The high electrical energy demand and the consumption of chemical reagents are common problems.

Physical methods
Different physical methods are also widely used, such as membrane-filtration processes (nanofiltration, reverse osmosis, electrodialysis, etc.) and adsorption techniques. The major disadvantage of the membrane processes is that they have a limited lifetime before membrane fouling occurs and the cost of periodic replacement must thus be included in any analysis of their economic viability.

Amongst the numerous techniques of dye removal, adsorption is the procedure of choice and gives the best results as it can be used to remove different types of coloring materials (Jain et al., 2003, Ho and McKay, 2003 and Derbyshire et al., 2001). If the adsorption system is designed correctly it will produce a high quality treated effluent. Most commercial systems currently use activated carbon as sorbent to remove dyes in wastewater because of its excellent adsorption ability. Activated carbon adsorption has been cited by the US Environmental Protection Agency as one of the best available control technologies (Derbyshire et al., 2001). However, although activated carbon is a preferred sorbent, its widespread use is restricted due to high cost. In order to decrease the cost of treatment, attempts have been made to find inexpensive alternative adsorbents.

Recently, numerous approaches have been studied for the development of cheaper and effective adsorbents. Many non-conventional low-cost adsorbents, including natural materials, biosorbents, and waste materials from industry and agriculture, have been proposed by several workers. These materials could be used as sorbents for the removal of dyes from solution. Some of the reported sorbents include clay materials (bentonite, kaolinite), zeolites, siliceous material (silica beads, alunite, perlite), agricultural wastes (bagasse pith, maize cob, rice husk, coconut shell), industrial waste products (waste carbon slurries, metal hydroxide sludge), biosorbents (chitosan, peat, biomass) and others (starch, cyclodextrin, cotton).

The most frequently used physicochemical method of textile wastewater treatment is coagulation. It is used mainly in wastewater decolorisation and reduction of the total load of suspensions and organic pollutants. The most popular is the coagulation with iron salts. The applied coagulant doses depend mainly on the type of wastewater and its reaction. They usually range from 300 to 5000 g/m3 wastewater. Using the processes of coagulation, a 40-70% reduction of COD and 40-60% colour reduction was obtained in the wastewater (Robinson etal 2001); thus, methods for decolorizing textile effluents are on the horizon. In recent years, many investigations have focused on several adsorbents; in particular, activated carbon for the removal of reactive dyes .

Synthesis of Nanoparticles

Generally, nanoparticles are prepared by a variety of chemical and physical methods such as chemical reduction (Yu, 2007; Tan et al., 2002; Petit et al., 1993; Vorobvova et al., 1999), photochemical reduction (Vorobvova et al., 1999; Mallick et al., 2005; Keki et al., 2000; Pileni, 2000; Sun et al., 2001), electrochemical reduction (Liu and Lin, 2004; Sandmann et al., 2000), heat vaporation (Bae et al., 2002; Smetana et al., 2005) etc.

These reagents could be inorganic such as sodium/potassium borohydrate, hydrazine and salts of tartarate, or organic ones like sodium citrate, ascorbic acid and amino acids capable of being oxidized. Various reagents have been reported to serve as stabilizing agent.

A number of reports adjusted the shape and size of silver nanoparticles using capping agents such as dendrimer, (Esumi et al., 2004) chitosan, (Murugadoss and Chattopadhyay, 2008) ionic liquid, (Zhang et al., 2009) and poly(vinylpyrrolidone) (PVP) (Sun and Xia, 2002), based on controlling the growth of silver nanoparticles through reaction confinement within the matrix or through preferential adsorption on specific crystal facets.
Most of these methods are extremely expensive and they also involve the use of toxic, hazardous chemicals which are not environmental friendly.

The biomedical applications of silver nanoparticle can be effective by the use of synthesized nanoparticles which minimize the factors such as toxicity and cost and are found to be exceptionally stable like other nanomaterials. Hence the development of better experimental procedures for the synthesis of nanoparticles of different chemical compositions, sizes, shapes and controlled polydispersity is vital for its advancement (Bhattacharya and Mukherjee, 2008).

Recently, a number of inorganic nanomaterials have been synthesized by bioreduction processes employing different microorganisms. Nanocrystals of gold, silver and their alloys have been synthesized within cells of lactic acid bacteria (Nair and Pradeep, 2002), Pseudomonas stutzeri AG259, (Joerger et al., 2000; Klaus et al., 2001)). In addition, eukaryotic organisms such as fungi have also been used to grow nanoparticles of different chemical composition and sizes like Verticillum sp. (Mukherjee et al., 2001); Fusarium oxysporum (Ahmad et al., 2003) and Aspergillus flavus (Vigneshwaran et al., 2007) and also with enzymes (Willner et al., 2006) On the other hand, to mimic natural biomineralization, even live plants have been studied as templates for silver nanoparticles synthesis (Sanghi and Verma, 2009).

Synthesis of Nanomaterials such as silver, gold, platinum and Pd using plants or plant extracts (Shankar et al., 2004) have been suggested as possible ecofriendly alternatives to chemical and physical methods. Nanoparticles synthesis using plants can be advantageous over other biological processes because it eliminates the elaborate process of maintaining cell cultures and can also be suitably scaled up for large-scale synthesis of nanoparticles (Shankar et al., 2004). Bioreduction of gold and silver ions to yield metal nanoparticles using living plants, (Gardea-Torresdey et al., 2003; Gardea-Torresdey et al., 2005), Geranium leaf broth (Shivshankar et al., 2003), Neem leaf broth, (Shivshankar et al., 2004) lemongrass extract (Shivshankar et al., 2005), Tamarind leaf extract (Ankamwar et al., 2005) and Aloe Vera plant extracts (Prathap et al., 2006), have been reported. Kasthuri et al., (2009) adopted a bioreductive approach of anisotropic gold and quasi-spherical silver nanoparticles by using apiin compound. Kasthuri et al.,(2009) synthesized the anisotropic gold and spherical- quasi-spherical silver nanoparticles using extract of phyllanthin at room temperature. Spent mushroom substrate (Vigneshwaran et al., 2007), Gliricidia sepium extract (Jae Yong Song and Beom Soo Kim, 2008; Raut Rajesh et al., 2009) and C. zeylanicum bark powder
(Sathishkumar et al., 2009) were used to synthesize nanoparticles. Krishna raj et al.,
(2010) studied the rapid synthesis of silver nanoparticles using aqueous leaves extract
of A. indica and evaluated its antibacterial activity against water borne pathogens such
as Escherichia coli and Vibrio cholerae. Daizy Philip (2009) studied mushroom mediated green chemistry approach towards the synthesis of gold, silver and gold-silver nanoparticles. Synthesis of metallic nanoparticles using green resources like Jatropha ( J. curcas latex) (Harekrishna Bar et al.2009), Hibiscus, (Daizy
Philip,2010), Ocimum tenuiflorum (Kiruba Daniel et al.,2011b) and Achyranthus aspera (Kiruba Daniel et al., 201 lc).

In this method a combination of all green routes are used for the synthesis of nanosolutions.

This inventive subject matter relates to novel nano metal solution and methods for using such nanopreparations for treating the effluent by precipitation. The present invention relates to new metal nanoparticles like silver, iron, copper etc substituted with various stabilizing agents like citrate, starch,polyol,etc .either alone or in combination with at least one additional agent, in desalting/decolouring. Nanosolution has been found to be superior to other techniques for water re-use in terms of initial cost, flexibility and simplicity of design, ease of operation and sensitivity to toxic pollutants. It does not require high electrical energy.

c) Written Description

Various both metal Nanoparticles were prepared using the above methods like citrate, starch and plant extract for different purpose either at room temperature or by heating at higher temperature. Pretreatment

An appropriate pretreatment system will reduce the load on subsequent treatment units and yield substantial savings in overall operating costs, especially chemicals. Pretreatment processes are usually designed to remove settleable solids from raw water before it is introduced into coagulation and rapid sand filters in the case of conventional treatment plants. There are several pretreatment processes available. The selection depends on a number of criteria such as cost, degree of treatment required, land availability, and climate Typical model is given in the flowchart

Treatment Technologies

There are 2 possible locations for treating the effluents, namely, at the textile factory or at the sewage works. The advantage of treatment at the factory is that it could allow for full re-use of water. The following technologies have all been used: coagulation and / or filtration through adsorbents (granular activated carbon, silica, clays, flyash, synthetic ion-exchange media, natural bioadsorbants, synthetic bioadsorbants), Since the effluent from the textile industry is complex and variable, it is unlikely that a single treatment technology will be suitable for total effluent treatment and water recycling.

Coagulation and/or Flocculation

Chemicals are added that form a precipitate which, either during its formation or as it settles, collects other contaminants. This precipitate is then removed either through
settling or by floating it to the surface and removing the sludge. This is a well-known
method of purifying water. Alum, lime, magnesium, iron salts and fly ash with clay
coagulants have been used to treat dye effluent to remove colour, both individually
and in combination with one another.

This inventive subject matter relates to the development of the combination of clay, fly ash and activated carbon and investigations into their use for removing initial pretreatment show promising results

The methods indicated for each process in are those that have been found to be the most suitable for that particular effluent stream. It highlights the importance of segregation of the various streams in order to treat them individually. Those effluent streams containing alkaline (mercerizing and bleaching) can be treated by one type of nanosolutions and reused in the same process. The same is true for other effluents as well and they can be recycled after filtration.

As mentioned previously, there is no one single treatment technology that can effectively treat the final effluent from the textile industry and a combination of the methods is necessary in order to achieve the required discharge standards.

SUMMARY OF THE INVENTION

Lit is an object of the present invention to provide a nanosolution wherein a various
nanoparticles like silver, iron, copper nickel ,chitosan etc and in combination with
various stabilizing agents like starch,citrate, various plant extracts like polyol etc

1. These nanopreparations either individually or in combination with various ratios like
silver, Iron and copper in 1:1:5 or other ratios depending upon effluent concentrations.

2. The invention disclosed herein relates to the formulation of nanosolution for effluent treatment in various combinations

3. In one embodiment the metal compounds are selected and another embodiment the reducing agents are selected and in another embodiment the stabilizing agents either plant or nonplant sources are selected . Another embodiment mixes the nanopreparations in various combinations for various purpose in effluent treatment.

4. In another embodiment the settled contaminants and clear supernatant water are reused for various purposes.

d) Drawings (where necessary)

f) Enablement and Best Mode

Complete specification.

The nanosolution is used in liquid form and /or solid form for effluent treatment.

h) Deposit (Microorganisms)

None

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5. CLAIMS (not applicable for provisional specification. Claims should start with the preamble — "l/we Claim" on separate page)

f) Enablement and Best Mode

Complete specification.

The nanosolution is used in liquid form and /or solid form for effluent treatment.

g) A .Claims

We claim that

l.The method of claim 1 that the metal compounds and the non metal compounds are used in the effluent treatment

2.The method of claim 1 that various nanoparticles are synthesized

3.The method of claim 1 various reducing and stabilizing agents used for synthesis.

4.The method of claim 2 that individual nanopreparations are used as nanosolution for effluent treatment.

5.The method of claim 3 that various combinations are mixed for nanosolution preparation for effluent treatment.

6.The method of claim 4 that nanosolutions are used in various forms like solid and liquid to suit the method and mode of treatment.

7.The method of claim 5 that reuse of settled waste for various purpose.

B.Claims

8. Method of synthesis of metal 1 nanopreparations using silver, iron, copper nanoparticles in various combinations.

9.Method of treating effluents for reusing the water, dye and nanoparticles.

C.Claims

10. Method of synthesis of metal nanopreparations using silver, iron, copper nanoparticles in various combinations using various green synthesis methods.

11.Method of treating effluents for reusing the water, dye and nanoparticles

12.Method of reusing the water and the sediment for other purpose.

What is claimed is:

13. A method of mixing various metal compounds in water and adding various reducing and stabilizing agents like citrate,starch and plant extracts

14. Mixing at room temperature or heating for one minute to ten minutes depending on the nanoparticle formation..

15. A method of removing dye and salt contaminant from effluents and sewages by nanosolution comprising any metal nanoparticles in single form or in mixture comprising the steps of:

16. Mixing the effluent or sewage comprising the dye, salt and other contaminant with nanosolution one in water in a tank to form a suspension and allowing to settle;

17. Filtering the suspension through a mesh to remove suspended materials; and reusing the water if suitable.

18. Mixing the nanosolution two if not suitable for reuse

19. Allowing the mixture of the precipitated salt and dye and the suspension to settle in the mixing tank for at least fifteen minutes to form a clear supernatant solution and a solid residue; and

20. Separating the clear supernatant solution from the solid residue comprising the dye contaminant and salt;

21. The method of claim 1, further comprising the steps of: recycling the clear supernatant solution;

22. Drying the solid residue comprising the dye and salt contaminant; grinding the dried solid residue comprising the nanoparticles with precipitated dye and salt contaminant; and

23. Adding fractions of acid in varying amounts to the dried solid residue to form a product for step down current products.