Title of Invention	"AN IMPROVED PROCESS FOR THE TREATMENT OF SPENT WASH USING MARIN ALGA TO PRODUCE POTABLE WATER"
Abstract	The present invention reports an improved process for the treatment of spent wash using marine alga to produce potable water which comprises contacting spent wash being diluted with water in the proportion ranging 1:1 to 1:5 with a marine red alga containing essentially, polysaccharides having sulfate/ acetyl functional group on cell wall & galactopyranose on their cell membrane and the proportion of diluted spent wash and the said alga being in the range of 100:0.25 to 100:1 for a period ranging 30-120 minutes preferably under stirring , treating the said reacted diluted spent wash with calcarious material in a proportion ranging 100:0.25 to 100:1 for a period ranging 30-120 minutes preferably under stirring, separating the coagulated material so formed from supernatant by conventional methods , then optionally treating the said supernatant by conventional ion exchange resin followed by activated charcoal to produce potable water

Title of Invention

"AN IMPROVED PROCESS FOR THE TREATMENT OF SPENT WASH USING MARIN ALGA TO PRODUCE POTABLE WATER"

Abstract

The present invention reports an improved process for the treatment of spent wash using marine alga to produce potable water which comprises contacting spent wash being diluted with water in the proportion ranging 1:1 to 1:5 with a marine red alga containing essentially, polysaccharides having sulfate/ acetyl functional group on cell wall & galactopyranose on their cell membrane and the proportion of diluted spent wash and the said alga being in the range of 100:0.25 to 100:1 for a period ranging 30-120 minutes preferably under stirring , treating the said reacted diluted spent wash with calcarious material in a proportion ranging 100:0.25 to 100:1 for a period ranging 30-120 minutes preferably under stirring, separating the coagulated material so formed from supernatant by conventional methods , then optionally treating the said supernatant by conventional ion exchange resin followed by activated charcoal to produce potable water

Full Text	This invention relates to an improved process for the treatment of spent wash using marine algae to produce potable water. This invention particularly relates to an improved method for separation of lignin and coloring matter from spent wash of alcohol industries using marine alga. The alcohol industry in India is based on molasses as the principal raw material. The alcohol recovery ranges from 7 to 9% from the molasses, fermentable sugars, the organic, inorganic chemicals in the molasses find their way into effluent which causes high BOD/COD. This effluent known as "spent wash" is also acidic in nature, forms hydrogen sulfide, creating bad odor having black color and hence cannot be disposed as such into the water stream. In the spent wash, origin of black color is due to plant pigment melanoidins, polyphenolic compounds, caramels, which are produced by thermal degradation and condensation reaction of sugar. In the prior art following methods are used for the separation of coloring bodies from spent wash in the alcohol industries. Several methods hitherto used are described in brief here in below: This is mainly useful to minimize industrial pollution due to the spent wash. Apparatus for the decolorizing molasses. Chida, T; Tsuboi, H. Jpn. Kokai. 77, 90, 639, 30 Jul. 1977,pp.3, CA 88 : 24490c.(1978) Molasses was decolorized with active carbon in an adsorption tower containing plate electrodes impressed with d. c. voltage. The pigments were dielec. Polarized by electrodes and adsorbed by active carbon. Thus molasses was decolorized 98% in an adsorption tower containing granular active carbon and vertical carbon electrodes at 10 cm intervals at 0.1 A/dm2 and 8V with retention time 3 h. Purification of molasses Kaga T; Hiramoto, T; Hamanaka, K; Sato, M. & Tokida Y. Jpn. Kokai 77, 108, 035. 10 Sept. 1977, pp.7,. CA 88: 75566q., (1978) Granular active carbon was used to decolorize brown liquors of Brix 62 - 3 and stammer color 5.2-5.4 was passed through a regenerated active column at 75-8C and solids carbon ratio 100 with 64% decolourization and molasses having Brix 35-6 pH 5.8 & stammer color 70 was passed through the same column at 72-3. Removal of coloring substances from molasses solutions. Shvets V N; Knogotkova F I; Pavyuchenko L N. Izv. Vyssh Uchebn. Zewed Pisheh. Technol. 1977, (4) 31-5, 88 : 8827n.,(1978). The filtration of molasses diluted to 35% with water through a column filled with AV - 16GS. (12626-33-4) Anion exchanger in chloride form removal >50% of colored substances and organic impurities. The effectiveness of removal of these substances decrease in order invert sugar > melanoidins > caramels. The decrease of molasses cone, improved its decolourization by exchanger. Colored substances in molasses could be coagulated by d. c. and removed by filtration but the procedure was effective only below 50% molasses cone, colored substances in molasses are not adsorbed by Soviet AGS - 4 activated carbon. Sorption of sugar coloring substances on ion exchangers. Wyroba A. Zesz. Nauk. Univ-Jagiellon Pr.Chem. 1976, 21_355-61. CA 88 : 8826 m.(1978) The decoloring power of ion exchange resin towards molasses (A) sugar from 3rd crystal (B) , thick syrup (C) and clear syrup (D) is not the same. Thus centranol. W -291 (I) (51258-00-5) and Amberlite IRA -900 (9050-97-9) reduce best the color of A & B or Amberlite IRA -68 II (9056-59-1) can be used for decolouring C & D is best decolorized by II, although Amberlite IRA- 4015 (9036-93-S) can also be used. A and C can be efficiently decolorized with carboraffina activated carbon. Methods for improved determination of sugar content in dark colored products of sugar industry Zagorulko A.Ya.; Boiko E.S.; Kcrobeinikova L.A.; Ponomarenko A.; Burlyai T.F. Sakh Prom-St 1978 (1) 65-6. CA 88 : 91344w.(1979) Colored substances present in the intermediate of sugar manufacture and molasses can be removed by combined treatment 1st with Pb (OAC) 4 (546- 67-8) and then with activated carbon. The decolorized solns. are made up to known vols. and used for the polarimetric/ polometric? detn. of sucrose (I) (57- 50-1). Activated carbon does not absorb (I) (87-50-1) and it does not require washing after it is filtered off. Waste water treatment. Sakurai, S. Jpn. Kokai Tokkyo Koho. 79 51,250. 21 April 1979. CA 91: 78574p.(1979) Hydrogen peroxide soln. is added to waste water, then the pH is adjusted to sol. pollutants. Adjusting the pH 6.0-8.5 flocculates the insoluble pollutants. In hitherto known processes main drawbacks are the use of acidic media which involves corrosive problems, filtration problems due to colloidal particles and incomplete removal of organics as well as inorganic matter in the effluent water and colored effluent water due to organic mainly lignin and mellanoidin. The adsorbing material used is activated carbon or commercially available chemo absorbents. The following references will be useful to assess the growth pattern of red algae in general and porphyra & liagora. Effect of effluent from sewage disposal plant of the growth of Porphyra. Ohgai, M.; sugimoto, T.; Murase, N.; Suisan, Z. 1994 42(1), 41-6.CA 121: 153004W. (1994) A laboratory culture study was made to examine the effect of effluent for sewage disposal plant on the growth of Porphyra and 4 species of diatoms. The culture media are prepared for different cons, of effluent. The growth of conchospores and thalli of Porphyra was slightly accelerated by the addition of effluent at 0.3-10.0%. Similar growth trend was observed in species of diatoms. Growth was suppressed at 30.0% effluent cone. Toxicity bio-assay of the municipal sewage effluents using Toshiro, M.; Akio, M.; Kankyo, M. 1993 16(5), 327-38, CA 119: 209657q. ( 1993) Bioassay techniques for testing treated wastewater and toxic chems. in seawater by monitoring seaweed growth are discussed. Strongest toxic substances for growth of Porpnyra were monochloramine resulting from chlorinated sewage. Studies on the effects of municipal waste water on the growth of Porphyra. Toshiro, M.; Kazuo, O.; Akio, A.; Tomao, Y.; Suisun, N.; 1988 54(10) CA 110 : 34929q.191989) Four kinds of chlorinated solutions were investigated to identify the causative substance inhibiting the growth of Porphyra yezoensis thalli. Inhibitory effects wee measured interms of length and no. of dead cells. Tests were conducted by cultures dosed with chlorinated municipal sewage effluent after nitrification and chlorinated ion exchange water respectively. Chloramine and chlorinated ion exchanged water was considered to be the causative substance in the gowth inhibition of Porphyra. Utilization of nitrogen and phosphorus from treated sewage and bay sediment by marine algae. Nobuyoshi, I.; Kunio, K.; Yuji, 0.; Takashi, N.; Zasshi, G.; 1987 42(1/2) CA 108;173165j.(1988) Porphyra yzoensis preferred NH4-N to NO3-N in the growth medium. But growth was affected when NH4-N level became >8 and 12mg/L resulting in rapid decrease of cell number and death of almost all cells at 32mg/L after 4 days. The bioaccumulation of metals by Rhodophyta sp. Malea, P.; Haritonidis, S.; Stratis, I. 1994 37(6), 505-13, CA 122 : 169365W.91995) The bioaccumulation of Fe, Cu, Zn, Cd, Pb, Na, K, Ca and Mg by seven species of red algae (Rhodophyta) were studied after their seasonal collections from 9 stations in Antikgra Gulf. This area is characterizes by its bauite substrate and discharge of wastes from an aluminum factory. No metal in Liagora showed a significant correlation with the concentration of the dissolved metals in seawater. Polysaccharide of algae 43 neutral xylan and sulfated xylomannan from red seaweed Usor, A. I.; Dobkina, I.M.; 1991 17(8) CA 115 : 275755p.(1992) A sulfated xylomannan and several fractions of neutral polysaccharides have been isolated from red alga Liagora. Water-soluble neutral xylan purified through copper complex was shown to be a linear polymer having B-1-4 and -3 linkages between D- xylopyranoseresidues at a ratio of 6:1. Ion sulfated polysaccharide was investigated using partial hydrolysis, methylation after and before desulfation as 13C NMR spectroscopy. Polysaccharide of algae Usov, A.I.; Dobkina, I.M. 1988 14(5), CA 109 :70387z.(1989) A sulfated xylomannan and several fractions of neutral polysaccharides were isolated from red seaweed Liagora. Xylomannan was shown to contain D-mannose and D-xylose of sulfate has a linear backbone built of alpha-1-3 linked d-mannopyranose residues. On the average there are two branching points and seven sulfate groups attached to position 6 & 2at a ratio of about 2:1 at every 14 mannopyranose residues of the main chain. Chemical study of Cuban seaweed Estevez, M. L; Olivan, D. L; Velazquez, R. 1985 1(1), 87-93, CA 104 : 165402m, (1986) Polysaccharides were examined from 13 species of red algae collected on Cuban coast. Sol. sulfated polysaccharides were predominated. The polysaccharides were primarily composed of galactose. These alga form a firm carrageenan gel when polysaccharide yield of >30% of dry weight were attained from alga. In the process of the present, lignin organic, sugars inorganic separated by treating the spent wash with seaweed's e.g. Porphyra, Liagora and calcarious material preferably lime powder. Seaweeds are the source of gel forming polysaccharides (phycocolloides) and widely used in the industries as emulsifying agents, gelling agents, stabilizers, thickeners and suspension agents. After carefully going through the literature search it is noticed that use of seaweed polysaccharide of Porphyra as a decolorizing agent is not mentioned. The combination Porphyra and lime powder found to remove organics, inorganics and the removal of the color of spent wash from black to pale yellow, which further treated with active carbon to get almost colorless liquid. Chemical structure of Liagora reveals the presence of a sulfated xylomannan; several fractions of neutral polysaccharides and other charged groups like mannans and xylans having phycocolloid properties and are anionic in nature. Polyelectrolytes with marked cation exchange properties must be of some significance in plants living in saline medium. The treated effluent was found to be passing BOD, COD and all the other parameters of effluent treated water required by the environmental agencies. All the operations in this process are done at room temperature, hence saves energy costs, the treated water can be recycled to the process. The resins used in the process can be generated with known methods. There is continued interest on development of new improved processes for separation of lignin organic matters; inorganic compounds from spent wash produces in the distillery wastes of sugar factories. It is the known fact that lignin-containing effluents are not degradable and hence has disposal problems in the environment. The invention is based on our finding that in the presence of Porphyra, p chemical structure 1,3 linked JMD-galactopyranose and 1,4 - linked 3,6 - anhydrous alpha - L -galactopyranose and other charged groups like mannans and xylans have better phycocolloid properties and are anionic polyelctrolytes with marked action exchange properties must be of some significance in plants living in saline medium. Further at pH >3 sulfated polysaccharide Porphyran, xylomannan, several fractions of neutral polysaccharides like D-xylopyranose, D-mannose and D-mannopyranose are responsible for the selective absorption of coloring chromophores and potassium with the adsorption of the lignin polyphonic bodies, the obtained pale yellow effluent treated with calcarious material particularly lime powder CaO > 98%, ion exchange system and activated carbon to remove organics, inorganics and trace of coloring matter to colorless water which can be recycled in the process in a period ranging upto 4-6 hours. The main object of the present invention is to provide an improved process for the treatment of spent wash from distillery wastes produced in the sugar industries to produce potable water using marine red alga. Another object is to treat the effluent in a manner to meet environmental standards. Yet another objective is to provide a process using red algae essentially having polysaccharide with sulfate or acetyl groups on cell wall and galactopyranose residue on cell membrane . Accordingly , the present invention provides an improved process for the treatment of spent wash using marine algae to produce potable water which comprises contacting spent wash being diluted with water in the proportion ranging 1:1 to 1:5 with a marine red algae for a period ranging 30-120 minutes preferably under stirring , treating the said reacted diluted spent wash with calcarious material for a period ranging 30-120 minutes preferably under stirring, separating the coagulated material so formed from supernatant by conventional methods , then optionally treating the said supernatant by conventional ion exchange resin such as herein described followed by activated charcoal to produce potable water In one of the embodiments of the present invention, marine red alga used may be either Porphyra or Liagora sp. In still another embodiments , the calcarious material such as lime, bone powder, shell powder, diatomaceous earth and salts of calcium and natural source thereof may be used. In another embodiments the black liquor may be diluted 5 times using water such as tap water, mineral water, natural water, demineralized water, distilled water . The ratio of Porphyra/Liagora and calcareous material powder to effluent may ranges from 0.5 - 2.00' The said alga used may be in the form of dried powder or embeded in neutral matrix or in a natural form. In another embodiment of the present invention the ion exchange resin is selected from anion/ cation exchanger resins such as commercially available IR-120, IR-400 and IRC-50. In a feature of the present invention the conventional methods used to separate the coagulated impurities may be sedimentation or filtration or centrifugation. In the feature of the present invention the treated effluent was found to be meeting all standards of the pollution control Act such as COD/BOD total dissolved solids & color. The final water produced is a colorless . In another feature of the present invention all operations of this process are done at room temperature without the use of mineral acid to make the effluent free from organic , inorganics and the treated water can be recycled to the process or let into the natural resource. The resin used in the process can be regenerated with known methods. The invention is described herein after, with reference to the following examples, which are illustrative only and should not be construed to the limit of the scope of present invention. Example -1 20ml of spent wash was diluted to 100ml with water and was contacted with Porphyra dried powder 1g. under stirring for 2hrs. followed by addition of lime powder 1.0g. The sludge separated was filtered and filtrate treated with Indion resin 20ml to bring its pH 2-3, the filtrate was again passed through column of IR-400 resin. The elute was passed over column of activated carbon 5g to colorless water with no organic matter. Color reduction was 89%. The initial COD of spent wash was 58032 .00 mg/L and after Porphyra and Lime treatment was brought down 4567.68mg/L and further to 12mg/L with ion exchange system and BOD of colorless water was 26. Example -2 20ml of spent wash was diluted to 100ml with water and was contacted with Porphyra dried powder 0.5gm. Under stirring for 2hrs. followed by addition of lime powder 0. 5gms. The sludge separated was filtered and filtrate treated with indion resin 20ml to bring its pH 2, 3 the filtrate was again passed through column of IR-400 resin. The elute was passed over column of activated carbon5g. to colorless water with no organic matter. Color reduction was 86 %. The initial COD of spent wash was 58032.00 mg/L and after Porphyra and Lime treatment was brought down to 3706.56 mg/L and further to 60mg/L with ion exchange system and BOD of colorless water was 20. Example -3 20ml of spent wash was diluted to 100ml with water and was contacted with Porphyra dried powder 0.25gm. Under stirring for 2hrs. followed by addition of lime powder 0.25gms. The sludge separated was filtered and filtrate treated with indion resin 20ml to bring its pH 2-3, the filtrate was again passed through column of IR-400 resin. The elute was passed over column of activated carbon 5g. to colorless water with no organic matter. Color reduction was 98%. The initial COD of spent wash was 58032.00mg/L and after Porphyra and Oyster treatment was brought down to 3600.29 mg/L and further to 88mg/L with ion exchange system and BOD of colorless water was 22. Example -4 20ml of spent wash was diluted to 100ml with water and was contacted with Liagora dried powder 1gm. under stirring for 2hrs. followed by addition of lime powder 1 .0gms. The sludge separated was filtered and filtrate treated with indion resin 20ml to bring its pH 2, 3 the filtrate was again passed through column of IR-400 resin. The elute was passed over column of activated carbonSg. to colorless water with no organic matter. Color reduction was 97%. The initial COD of spent wash was 58032.OOmg/L and after Liagora and Oyster treatment was brought down to 1235.52mg/L and further to 12mg/L with ion exchange system and BOD of colorless water was 26. Example -5 20ml of spent wash was diluted to 100ml with water and was contacted with Liagora dried powder 0.5gm. under stirring for 2hrs. followed by addition of lime powder 0. 5gms. The sludge separated was filtered and filtrate treated with indion resin 20ml to bring its pH 2, 3 the filtrate was again passed through column of IR-400 resin. The elute was passed over column of activated carbon5g. to colorless water with no organic matter. Color reduction was 94 %. The initial COD of spent wash was 58032.00mg/L and after Liagora and Lime treatment was brought down to 1834.56mg/L and further to 60mg/L with ion exchange system and BOD of colorless water was 20. Example -6 20ml of spent wash was diluted to 100ml with water and was contacted with Liagora dried powder 0.25gm. Under stirring for 2hrs. followed by addition of lime powder 0.25gms. The sludge separated was filtered and filtrate treated with indion resin 20ml to bring its pH 2-3, the filtrate was again passed through column of IR-400 resin. The elute was passed over column of activated carbonSg. to colorless water with no organic matter. Color reduction was 88%. The initial COD of spent wash was 58032.00mg/L and after Liagora and lime treatment was brought down to 2000.07mg/L and further to'88mg/L with ion exchange system and BOD of colorless water was 22. As illustrated above all other materials indicated in objectives & embodiments are found equally effective though not illustrated by the examples. The advantages of the present invention are as follows: 1. The process of the present invention is cost effective & environment friendly. 2. It makes use of natural resources which are degradable biologically and not harmful to the ecosystem. 3. The process results in producing colorless, potable water which meets all the environment control Board stipulated standards. 4. The water thus produced either can be useful for recycling in the process or let into the natural resources. We have another application vide no 1085/DEL/1999 which is co pending with the present application . In the said co-pending application the invention is about the improved process for the treatment of agro based black liquor preferably from the papermill waste using marine algae to produce potable water. We claim : 1. An improved process for the treatment of spent wash using marine algae to produce potable water which comprises contacting spent wash being diluted with water in the proportion ranging 1:1 to 1:5 with a marine red algae for a period ranging 30-120 minutes preferably under stirring , treating the said reacted diluted spent wash with calcarious material for a period ranging 30-120 minutes preferably under stirring, separating the coagulated material so formed from supernatant by conventional methods , then optionally treating the said supernatant by conventional ion exchange resin such as herein described followed by activated charcoal to produce potable water. 2. An improved process as claimed in claim 1, wherein the marine red alga used is Porphyra or Liagora sp. 3. An improved process as claimed in claim 1-2, wherein the calcarious material used is lime, bone powder, shell powder, diatomaceous earth, salts of calcium and natural source thereof. 4. An improved process as claimed in claim 1-3, wherein the spent wash is diluted using water such as tap water, mineral water, natural water, demineralized water, distilled water . 5. An improved process as claimed in claim 1- 4, wherein the said alga is used in the form of dry powder, embedded in neutral matrix, or natural form. 6. An improved process as claimed in claim 1- 6, wherein the separation of coagulated material is carried out by sedimentation, filtration, centrifugation under condition such as herein described . 7. An improved process for the treatment of spent wash using marine alga to produce potable water substantially as herein described with reference to the examples.

Full Text

This invention relates to an improved process for the treatment of spent wash using marine algae to produce potable water.
This invention particularly relates to an improved method for separation of lignin and coloring matter from spent wash of alcohol industries using marine alga.
The alcohol industry in India is based on molasses as the principal raw material. The alcohol recovery ranges from 7 to 9% from the molasses, fermentable sugars, the organic, inorganic chemicals in the molasses find their way into effluent which causes high BOD/COD. This effluent known as "spent wash" is also acidic in nature, forms hydrogen sulfide, creating bad odor having black color and hence cannot be disposed as such into the water stream. In the spent wash, origin of black color is due to plant pigment melanoidins, polyphenolic compounds, caramels, which are produced by thermal degradation and condensation reaction of sugar.
In the prior art following methods are used for the separation of coloring bodies from spent wash in the alcohol industries. Several methods hitherto used are described in brief here in below:
This is mainly useful to minimize industrial pollution due to the spent wash.
Apparatus for the decolorizing molasses.
Chida, T; Tsuboi, H. Jpn. Kokai. 77, 90, 639, 30 Jul. 1977,pp.3, CA 88 : 24490c.(1978)
Molasses was decolorized with active carbon in an adsorption tower containing plate electrodes impressed with d. c. voltage. The pigments were dielec. Polarized by electrodes and adsorbed by active carbon. Thus

molasses was decolorized 98% in an adsorption tower containing granular
active carbon and vertical carbon electrodes at 10 cm intervals at 0.1 A/dm2
and 8V with retention time 3 h.
Purification of molasses
Kaga T; Hiramoto, T; Hamanaka, K; Sato, M. & Tokida Y. Jpn. Kokai 77, 108,
035. 10 Sept. 1977, pp.7,. CA 88: 75566q., (1978)
Granular active carbon was used to decolorize brown liquors of Brix 62 - 3
and stammer color 5.2-5.4 was passed through a regenerated active column
at 75-8C and solids carbon ratio 100 with 64% decolourization and molasses
having Brix 35-6 pH 5.8 & stammer color 70 was passed through the same
column at 72-3.
Removal of coloring substances from molasses solutions.
Shvets V N; Knogotkova F I; Pavyuchenko L N. Izv. Vyssh Uchebn. Zewed
Pisheh.
Technol. 1977, (4) 31-5, 88 : 8827n.,(1978).
The filtration of molasses diluted to 35% with water through a column filled
with AV - 16GS. (12626-33-4) Anion exchanger in chloride form removal
>50% of colored substances and organic impurities. The effectiveness of
removal of these substances decrease in order invert sugar > melanoidins >
caramels. The decrease of molasses cone, improved its decolourization by
exchanger. Colored substances in molasses could be coagulated by d. c. and
removed by filtration but the procedure was effective only below 50%
molasses cone, colored substances in molasses are not adsorbed by Soviet
AGS - 4 activated carbon.
Sorption of sugar coloring substances on ion exchangers.

Wyroba A. Zesz. Nauk. Univ-Jagiellon Pr.Chem. 1976, 21_355-61. CA 88 :
8826 m.(1978)
The decoloring power of ion exchange resin towards molasses (A) sugar from
3rd crystal (B) , thick syrup (C) and clear syrup (D) is not the same. Thus
centranol. W -291 (I) (51258-00-5) and Amberlite IRA -900 (9050-97-9)
reduce best the color of A & B or Amberlite IRA -68 II (9056-59-1) can be
used for decolouring C & D is best decolorized by II, although Amberlite IRA-
4015 (9036-93-S) can also be used. A and C can be efficiently decolorized
with carboraffina activated carbon.
Methods for improved determination of sugar content in dark colored
products of sugar industry
Zagorulko A.Ya.; Boiko E.S.; Kcrobeinikova L.A.; Ponomarenko A.; Burlyai
T.F. Sakh
Prom-St 1978 (1) 65-6. CA 88 : 91344w.(1979)
Colored substances present in the intermediate of sugar manufacture and
molasses can be removed by combined treatment 1st with Pb (OAC) 4 (546-
67-8) and then with activated carbon. The decolorized solns. are made up to
known vols. and used for the polarimetric/ polometric? detn. of sucrose (I) (57-
50-1). Activated carbon does not absorb (I) (87-50-1) and it does not require
washing after it is filtered off.
Waste water treatment.
Sakurai, S. Jpn. Kokai Tokkyo Koho. 79 51,250. 21 April 1979. CA 91:
78574p.(1979) Hydrogen peroxide soln. is added to waste water, then the pH
is adjusted to sol. pollutants. Adjusting the pH 6.0-8.5 flocculates the insoluble pollutants.

In hitherto known processes main drawbacks are the use of acidic media which involves corrosive problems, filtration problems due to colloidal particles and incomplete removal of organics as well as inorganic matter in the effluent water and colored effluent water due to organic mainly lignin and mellanoidin.
The adsorbing material used is activated carbon or commercially available chemo absorbents.
The following references will be useful to assess the growth pattern of red algae in general and porphyra & liagora.
Effect of effluent from sewage disposal plant of the growth of Porphyra. Ohgai, M.; sugimoto, T.; Murase, N.; Suisan, Z. 1994 42(1), 41-6.CA 121: 153004W. (1994)
A laboratory culture study was made to examine the effect of effluent for sewage disposal plant on the growth of Porphyra and 4 species of diatoms. The culture media are prepared for different cons, of effluent. The growth of conchospores and thalli of Porphyra was slightly accelerated by the addition of effluent at 0.3-10.0%. Similar growth trend was observed in species of diatoms. Growth was suppressed at 30.0% effluent cone. Toxicity bio-assay of the municipal sewage effluents using
Toshiro, M.; Akio, M.; Kankyo, M. 1993 16(5), 327-38, CA 119: 209657q. ( 1993) Bioassay techniques for testing treated wastewater and toxic chems. in seawater by monitoring seaweed growth are discussed. Strongest toxic substances for growth of Porpnyra were monochloramine resulting from chlorinated sewage.

Studies on the effects of municipal waste water on the growth of Porphyra.
Toshiro, M.; Kazuo, O.; Akio, A.; Tomao, Y.; Suisun, N.; 1988 54(10) CA 110 :
34929q.191989)
Four kinds of chlorinated solutions were investigated to identify the causative
substance inhibiting the growth of Porphyra yezoensis thalli. Inhibitory effects
wee measured interms of length and no. of dead cells. Tests were conducted
by cultures dosed with chlorinated municipal sewage effluent after nitrification
and chlorinated ion exchange water respectively. Chloramine and chlorinated
ion exchanged water was considered to be the causative substance in the
gowth inhibition of Porphyra.
Utilization of nitrogen and phosphorus from treated sewage and bay
sediment by marine algae.
Nobuyoshi, I.; Kunio, K.; Yuji, 0.; Takashi, N.; Zasshi, G.; 1987 42(1/2) CA
108;173165j.(1988)
Porphyra yzoensis preferred NH4-N to NO3-N in the growth medium. But
growth was affected when NH4-N level became >8 and 12mg/L resulting
in rapid decrease of cell number and death of almost all cells at 32mg/L after
4 days.
The bioaccumulation of metals by Rhodophyta sp.
Malea, P.; Haritonidis, S.; Stratis, I. 1994 37(6), 505-13, CA 122 :
169365W.91995)
The bioaccumulation of Fe, Cu, Zn, Cd, Pb, Na, K, Ca and Mg by seven
species of red algae (Rhodophyta) were studied after their seasonal
collections from 9 stations in Antikgra Gulf. This area is characterizes by its

bauite substrate and discharge of wastes from an aluminum factory. No metal in Liagora showed a significant correlation with the concentration of the dissolved metals in seawater.
Polysaccharide of algae 43 neutral xylan and sulfated xylomannan from red seaweed
Usor, A. I.; Dobkina, I.M.; 1991 17(8) CA 115 : 275755p.(1992) A sulfated xylomannan and several fractions of neutral polysaccharides have been isolated from red alga Liagora. Water-soluble neutral xylan purified through copper complex was shown to be a linear polymer having B-1-4 and -3 linkages between D- xylopyranoseresidues at a ratio of 6:1. Ion sulfated polysaccharide was investigated using partial hydrolysis, methylation after and before desulfation as 13C NMR spectroscopy. Polysaccharide of algae
Usov, A.I.; Dobkina, I.M. 1988 14(5), CA 109 :70387z.(1989) A sulfated xylomannan and several fractions of neutral polysaccharides were isolated from red seaweed Liagora. Xylomannan was shown to contain D-mannose and D-xylose of sulfate has a linear backbone built of alpha-1-3 linked d-mannopyranose residues. On the average there are two branching points and seven sulfate groups attached to position 6 & 2at a ratio of about 2:1 at every 14 mannopyranose residues of the main chain. Chemical study of Cuban seaweed
Estevez, M. L; Olivan, D. L; Velazquez, R. 1985 1(1), 87-93, CA 104 : 165402m, (1986)
Polysaccharides were examined from 13 species of red algae collected on Cuban coast.

Sol. sulfated polysaccharides were predominated. The polysaccharides were primarily composed of galactose. These alga form a firm carrageenan gel when polysaccharide yield of >30% of dry weight were attained from alga.
In the process of the present, lignin organic, sugars inorganic separated by treating the spent wash with seaweed's e.g. Porphyra, Liagora and calcarious material preferably lime powder.
Seaweeds are the source of gel forming polysaccharides (phycocolloides) and widely used in the industries as emulsifying agents, gelling agents, stabilizers, thickeners and suspension agents. After carefully going through the literature search it is noticed that use of seaweed polysaccharide of Porphyra as a decolorizing agent is not mentioned. The combination Porphyra and lime powder found to remove organics, inorganics and the removal of the color of spent wash from black to pale yellow, which further treated with active carbon to get almost colorless liquid.
Chemical structure of Liagora reveals the presence of a sulfated xylomannan; several fractions of neutral polysaccharides and other charged groups like mannans and xylans having phycocolloid properties and are anionic in nature. Polyelectrolytes with marked cation exchange properties must be of some significance in plants living in saline medium. The treated effluent was found to be passing BOD, COD and all the other parameters of effluent treated water required by the environmental agencies.
All the operations in this process are done at room temperature, hence saves energy costs, the treated water can be recycled to the process. The resins used in the process can be generated with known methods.

There is continued interest on development of new improved processes for separation of lignin organic matters; inorganic compounds from spent wash produces in the distillery wastes of sugar factories. It is the known fact that lignin-containing effluents are not degradable and hence has disposal problems in the environment.
The invention is based on our finding that in the presence of Porphyra,
p chemical structure 1,3 linked JMD-galactopyranose and 1,4 - linked 3,6 -
anhydrous alpha - L -galactopyranose and other charged groups like mannans and xylans have better phycocolloid properties and are anionic polyelctrolytes with marked action exchange properties must be of some significance in plants living in saline medium.
Further at pH >3 sulfated polysaccharide Porphyran, xylomannan, several fractions of neutral polysaccharides like D-xylopyranose, D-mannose and D-mannopyranose are responsible for the selective absorption of coloring chromophores and potassium with the adsorption of the lignin polyphonic bodies, the obtained pale yellow effluent treated with calcarious material particularly lime powder CaO > 98%, ion exchange system and activated carbon to remove organics, inorganics and trace of coloring matter to colorless water which can be recycled in the process in a period ranging upto 4-6 hours.
The main object of the present invention is to provide an improved process for the treatment of spent wash from distillery wastes produced in the sugar industries to produce potable water using marine red alga.
Another object is to treat the effluent in a manner to meet environmental standards.

Yet another objective is to provide a process using red algae essentially having polysaccharide with sulfate or acetyl groups on cell wall and galactopyranose residue on cell membrane .
Accordingly , the present invention provides an improved process for the treatment of spent wash using marine algae to produce potable water which comprises contacting spent wash being diluted with water in the proportion ranging 1:1 to 1:5 with a marine red algae for a period ranging 30-120 minutes preferably under stirring , treating the said reacted diluted spent wash with calcarious material for a period ranging 30-120 minutes preferably under stirring, separating the coagulated material so formed from supernatant by conventional methods , then optionally treating the said supernatant by conventional ion exchange resin such as herein described followed by activated charcoal to produce potable water
In one of the embodiments of the present invention, marine red alga used may be either Porphyra or Liagora sp.
In still another embodiments , the calcarious material such as lime, bone powder, shell powder, diatomaceous earth and salts of calcium and natural source thereof may be used.
In another embodiments the black liquor may be diluted 5 times using water such as tap water, mineral water, natural water, demineralized water, distilled water .

The ratio of Porphyra/Liagora and calcareous material powder to effluent may ranges from 0.5 - 2.00'
The said alga used may be in the form of dried powder or embeded in neutral matrix or in a natural form.
In another embodiment of the present invention the ion exchange resin is selected from anion/ cation exchanger resins such as commercially available IR-120, IR-400 and IRC-50.
In a feature of the present invention the conventional methods used to separate the coagulated impurities may be sedimentation or filtration or centrifugation.
In the feature of the present invention the treated effluent was found to be meeting all standards of the pollution control Act such as COD/BOD total dissolved solids & color. The final water produced is a colorless .
In another feature of the present invention all operations of this process are done at room temperature without the use of mineral acid to make the effluent free from organic , inorganics and the treated water can be recycled to the process or let into the natural resource.
The resin used in the process can be regenerated with known methods.
The invention is described herein after, with reference to the following examples, which are illustrative only and should not be construed to the limit of the scope of present invention. Example -1
20ml of spent wash was diluted to 100ml with water and was contacted with Porphyra dried powder 1g. under stirring for 2hrs. followed by addition of lime

powder 1.0g. The sludge separated was filtered and filtrate treated with Indion resin 20ml to bring its pH 2-3, the filtrate was again passed through column of IR-400 resin. The elute was passed over column of activated carbon 5g to colorless water with no organic matter. Color reduction was 89%. The initial COD of spent wash was 58032 .00 mg/L and after Porphyra and Lime treatment was brought down 4567.68mg/L and further to 12mg/L with ion exchange system and BOD of colorless water was 26. Example -2
20ml of spent wash was diluted to 100ml with water and was contacted with Porphyra dried powder 0.5gm. Under stirring for 2hrs. followed by addition of lime powder 0. 5gms. The sludge separated was filtered and filtrate treated with indion resin 20ml to bring its pH 2, 3 the filtrate was again passed through column of IR-400 resin. The elute was passed over column of activated carbon5g. to colorless water with no organic matter. Color reduction was 86 %. The initial COD of spent wash was 58032.00 mg/L and after Porphyra and Lime treatment was brought down to 3706.56 mg/L and further to 60mg/L with ion exchange system and BOD of colorless water was 20. Example -3
20ml of spent wash was diluted to 100ml with water and was contacted with Porphyra dried powder 0.25gm. Under stirring for 2hrs. followed by addition of lime powder 0.25gms. The sludge separated was filtered and filtrate treated with indion resin 20ml to bring its pH 2-3, the filtrate was again passed through column of IR-400 resin. The elute was passed over column of activated carbon 5g. to colorless water with no organic matter. Color reduction was 98%. The initial COD of spent wash was 58032.00mg/L and after

Porphyra and Oyster treatment was brought down to 3600.29 mg/L and further to 88mg/L with ion exchange system and BOD of colorless water was 22.
Example -4
20ml of spent wash was diluted to 100ml with water and was contacted with Liagora dried powder 1gm. under stirring for 2hrs. followed by addition of lime powder 1 .0gms. The sludge separated was filtered and filtrate treated with indion resin 20ml to bring its pH 2, 3 the filtrate was again passed through column of IR-400 resin. The elute was passed over column of activated carbonSg. to colorless water with no organic matter. Color reduction was 97%. The initial COD of spent wash was 58032.OOmg/L and after Liagora and Oyster treatment was brought down to 1235.52mg/L and further to 12mg/L with ion exchange system and BOD of colorless water was 26. Example -5
20ml of spent wash was diluted to 100ml with water and was contacted with Liagora dried powder 0.5gm. under stirring for 2hrs. followed by addition of lime powder 0. 5gms. The sludge separated was filtered and filtrate treated with indion resin 20ml to bring its pH 2, 3 the filtrate was again passed through column of IR-400 resin. The elute was passed over column of activated carbon5g. to colorless water with no organic matter. Color reduction was 94 %. The initial COD of spent wash was 58032.00mg/L and after Liagora and Lime treatment was brought down to 1834.56mg/L and further to 60mg/L with ion exchange system and BOD of colorless water was 20. Example -6 20ml of spent wash was diluted to 100ml with water and was contacted with

Liagora dried powder 0.25gm. Under stirring for 2hrs. followed by addition of lime powder 0.25gms. The sludge separated was filtered and filtrate treated with indion resin 20ml to bring its pH 2-3, the filtrate was again passed through column of IR-400 resin. The elute was passed over column of activated carbonSg. to colorless water with no organic matter. Color reduction was 88%. The initial COD of spent wash was 58032.00mg/L and after Liagora and lime treatment was brought down to 2000.07mg/L and further to'88mg/L with ion exchange system and BOD of colorless water was 22.
As illustrated above all other materials indicated in objectives & embodiments are found equally effective though not illustrated by the examples.
The advantages of the present invention are as follows:
1. The process of the present invention is cost effective & environment
friendly.
2. It makes use of natural resources which are degradable biologically
and not harmful to the ecosystem.
3. The process results in producing colorless, potable water which meets
all the environment control Board stipulated standards.
4. The water thus produced either can be useful for recycling in the
process or let into the natural resources.
We have another application vide no 1085/DEL/1999 which is co pending with the present application . In the said co-pending application the invention is about the improved process for the treatment of agro based black liquor preferably from the papermill waste using marine algae to produce potable water.

We claim :
1. An improved process for the treatment of spent wash using marine
algae to produce potable water which comprises contacting spent
wash being diluted with water in the proportion ranging 1:1 to 1:5
with a marine red algae for a period ranging 30-120 minutes
preferably under stirring , treating the said reacted diluted spent
wash with calcarious material for a period ranging 30-120 minutes
preferably under stirring, separating the coagulated material so formed
from supernatant by conventional methods , then optionally treating
the said supernatant by conventional ion exchange resin such as herein
described followed by activated charcoal to produce potable water.
2. An improved process as claimed in claim 1, wherein the marine red
alga used is Porphyra or Liagora sp.
3. An improved process as claimed in claim 1-2, wherein the calcarious
material used is lime, bone powder, shell powder, diatomaceous earth,
salts of calcium and natural source thereof.
4. An improved process as claimed in claim 1-3, wherein the spent wash
is diluted using water such as tap water, mineral water, natural water,
demineralized water, distilled water .

5. An improved process as claimed in claim 1- 4, wherein the said alga
is used in the form of dry powder, embedded in neutral matrix, or
natural form.
6. An improved process as claimed in claim 1- 6, wherein the separation
of coagulated material is carried out by sedimentation, filtration,
centrifugation under condition such as herein described .

7. An improved process for the treatment of spent wash using marine alga to produce potable water substantially as herein described with reference to the examples.

Documents:

1086-del-1999-abstract.pdf

1086-del-1999-claims.pdf

1086-del-1999-correspondence-others.pdf

1086-del-1999-correspondence-po.pdf

1086-del-1999-description (complete).pdf

1086-del-1999-form-1.pdf

1086-del-1999-form-19.pdf

1086-del-1999-form-2.pdf

1086-del-1999-form-3.pdf

1086-del-1999-petition-138.pdf

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Patent Number

215771

Indian Patent Application Number

1086/DEL/1999

PG Journal Number

12/2008

Publication Date

21-Mar-2008

Grant Date

03-Mar-2008

Date of Filing

10-Aug-1999

Name of Patentee

COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH

Applicant Address

RAFI MARG, NEW DELHI - 110 001

Inventors:

#	Inventor's Name	Inventor's Address
1	PRAMOD PRABHAKAR MOGHE	NATIONAL CHEMICAL LABORATORY PUNE- 411 008
2	VINITA VINAY PANCHANDIKAR	NATIONAL CHEMICAL LABORATORY PUNE- 411 008
3	ARVIND GAJANAN UNTAWALE	NATIONAL INSTITUTE OF OCEANOGRAPHY, DONA PAULA, GOA - 403 004
4	VINOD KASHINATH DHARGALKAR	NATIONAL INSTITUTE OF OCEANOGRAPHY, DONA PAULA, GOA - 403 004

PCT International Classification Number

D21C 11/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA