Title of Invention	AN IMPROVED PROCESS FOR THE TREATMENT OF AGRO BASED BLACK LIQUOR WASTE TO PRODUCE POTABLE WATER
Abstract	This invention relates to an improved process for the treatment of agro based black liquor waste to produce potable water. The process treats black liquor from paper mils by removing organics, lignin and coloring matter using biological material. Process steps comprises: contacting at least 1:1 diluted the said black liquor with a marine red alga in the form of dry powder embeded in neutral matrix or natural form containing essentially, polysaccharides having sulfate/acetyl functional group on cell wall & galactopyrandse on their cell membrane, at least for a period of 30 minutes preferably under stirring, treating with conventional calcarious material at least for 30 minutes preferably under stirring, seperating the coagulated material so formed from supernatant by conventional methods, 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 AGRO BASED BLACK LIQUOR WASTE TO PRODUCE POTABLE WATER

Abstract

This invention relates to an improved process for the treatment of agro based black liquor waste to produce potable water. The process treats black liquor from paper mils by removing organics, lignin and coloring matter using biological material. Process steps comprises: contacting at least 1:1 diluted the said black liquor with a marine red alga in the form of dry powder embeded in neutral matrix or natural form containing essentially, polysaccharides having sulfate/acetyl functional group on cell wall & galactopyrandse on their cell membrane, at least for a period of 30 minutes preferably under stirring, treating with conventional calcarious material at least for 30 minutes preferably under stirring, seperating the coagulated material so formed from supernatant by conventional methods, 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 Agro based black liquor waste to produce potable water. More particularly the invention relates to an improved process for treatment of black liquors from paper mills by removing organic and inorganic matter, lignin and coloring matter using marine biological material. Lignin may be defined as amorphous polyphenolic material arising from an enzyme mediated dehydrogenative polymerization of three phenylpropanoid monomers, of e.g. conyferyl, sinapyl and p-coumaryl alcohols. Lignin (from the Latin lignum, wood) after cellulose is the principal constituent of woody structure of higher plants in part deposited in xylem cell walls, in part located in the intercellular spaces. The sulfite waste liquors from paper mills contain upto 3 to 6% lignin, which are not easily biodegradable. This lignin may act as a source of vanillin, syringic aldehyde, can be used as extender for phenolic plastics as well as to strengthen the rubber, as oil mud additive to stabilize asphalt, as emulsions to precipitate proteins. Lignin also can be converted to pure low molecular weight chemicals; it may serve as an important feedstock for the chemical industry. At present only vanillin and dimethyl sulfide are produced commercially and economically, However, competitive processes for conversion of lignin to phenolic and aromatic chemicals are real possibilities. Until the past 2-3 decades or so, large amounts of lignin were discarded into streams and waterways as dilute aqueous solutions which is not tolerated now and almost all waste streams containing lignin are concentrated and burned. The process of the present invention is environment friendly & convert hazardous waste to a potable water and helps in preserving environment as per environmental pollution act. In order to conform to environmental quality guidelines, a number primary and secondary treatment systems to control effluents are installed; treatment comprises clarifires to remove 85-1 OOwt. % of solid such as clarifires in first treatment and lagoons aerated or otherwise, trickling filters, modified biological systems, charcoal treatment etc. to remove as 90-95% of BOD, most solid, most of the toxicity except very little color. Ultrafiltrations also has been tried and found futile to remove total dissolved solids completely. The pulp and paper industry uses large amounts of water which is recycled and reused resulting in temperature rise and dissolution of more solids in water enhancing problems e.g. corrosion, slime and other deposits. Directly or indirectly all of these viz. BOD, color and toxicity may effect aquatic life. Total dissolved solids are removed and used as energy source in fuel. Biomethanation has also been attempted. All these do not meet the standards of pollution control. Therefore it becomes very essential to remove color, total dissolved solids with negligible quantity of BOD and COD. In the prior art following methods are used for the separation of lignin from black liquor in paper industry. Several methods hitherto used are described in brief herein bellow: Purification of waste waters for installation of bleaching sulfate paper Udeleholms A.B. Fr. Demande 2, 202,043 03 May 1974. Swed Appl. 12772/72 04 Oct. CA 82: 34833 g (1975). The lignin and other organic matter are mostly precipitated from wastewater by addition of mineral acid and by filtration. The filtered wastewater is treated with feebly alkaline ion exchange resin activated with acid and then resin is eluted with alkali to remove adsorbed lignin. The elute together with solution of original precipitate in alkali are recycled to the sulfate pulp process, preferably by burning in the black liquor recovery process. In this process the ion exchange resins used are commercially available chemical components. Desulfurisation of waste gas with pulp waste liquor Suyama A; Hayashi, H (Mitsubishi Kausha Ltd. Toyo Tokushi Kogyo K. K.) Jap. Kokai 76,20,089 17 Feb. 1976. CA 85: 67527a 9(1976). Fiber free black liquor is used for waste gas desulfurisation and lignin in waste liquor is precipitated as lignin sulfate. The fiber is removed by boiling. Thus 1100 ppm S02 containing diesel oil boiler flue gas was desulfurised with boiled black liquor (pH 12) to desulfurise 93%. The spent liquor was air oxidized and coagulant was added to precipitate lignin and others. Recovery of sodium hydroxide and black liquor from cellulose manufacture Torras hostench S. A. Belg. 861, 585 31 March 1977. Span Appl. 461, 364 04 Aug. 1977. CA 89: 61292 (1978). An improved process for title recovery as compared to Spanish patent No. 29, 158 comprises carbonation of spent liquor (preconcentrated to 40% from 10-15%) from treatment of pulp by bubbling C02 through a stream of spent liquor in a counter current system from bottom to the top of the liquor at 75-85 and 0.5kg/cm2 and treating the resulting silica -lignin precipitate with 0.03 N NaOH to redissolve the lignin for recycling to carbonated black liquor before further concentrating by evaporating. Recovery of inorganic compounds from Kraft pulping black liquors Domtar Inc. Jpn. Kokai Tokkyo Koho 58 36292 (83 36292) 03 Marc. 1985. Appl.382387 23 July 1981. CA 99: 89814 h (1983). Sodium compound from Kraft pulping black liquors are recovered by first acidifying the cool liquor with acids containing HaS04 to Kraft black liquor by ultracentrifugation (DC) of liquor, followed by electrodialysis (E) of UC permeate, treating deionate from electrodialysis with acid to precipitate lignin and electrolytic H20 splitting of resulting solution. Removal of lignin alkaline waste pulping liquors Ishikawa H.; Kade K. (Oji Paper Co. Ltd.). Jpn. Kokai Tokkyo JP 62 90398 (87 90 389) 24th April 1987 85 226 870 Oct. 1985. CA 107: 79 808 d (1987). The title removal involved colloidising the solution lignin followed by ultrafiltration. Thus beech chips were cooked at effective alkali 14% sulfidity 25%, liquor ratio 4 and 165. The resulting black liquor was filtered, adjusted to pH 11,10 and 9 with which CO2and ultra filtered to give delignification 89%, 94% and 97% respectively. Manufacture of methylolated lignin from black Kraft liquor residues Diliing Peter (West Vaco Corp.) US 4, 764,59716 Aug. 1988 Appl. 61 460 15 Jun 1987 CA 109: 212612v (1988). Methylolated lignin is manufactured from black Kraft liquor residues by initially oxidizing black Kraft liquor containing lignin and salt in situ methylolation of lignin with an aldehyde followed by lowering the pH of the black Kraft liquor residue to precipitate methylolated lignin and finally recovering the precipitated methylolated lignin from black liquor residue. Thus a black Kraft residue (pH 13) was oxidized with air until the Na2S content was 1% and then stirred with 31b/mole HCHO/1000 Ib lignin at 70 for 2h. The black liquor containing methylolated lignin was acidified with HaS04 to pH4. The methylolated lignin was coagulated, filtered, washed with water. The methylolated slurry was then treated with triethanolamine to pH7 and then sulfonated with S02 at 205°F for 12h to give sulfomethylolated amine salt useful as dispersent for azodyes. Recovery of solids from black liquors Caperos, S.A. Span ES 2, 006, 964 16 May 1989 Appl. 8, 801,697 27 May 1988. CA 114: 26042 n (1991). Solids in black liquors are recovered, as precipitate by mixing 1 part black liquor with 0.1-1.0 parts reactive precipitating agent and separating the precipitate. The black liquor electrodialysed globules was mixed with equal volume of saturated solution of CaCI2 in EtOH to form precipitate which was separated with centrifuged and washed with 1:1 EtOH- water to give precipitate 134 parts, organic components 105 parts, lignin 53 parts and pentosans 8g with 85% yield. Areding process of paper black liquor with sulfur-dioxide Sun, L; Xu, Mu, H et al (Chinese Academy of Sciences, environment-estimating department). Faming Zhuangli Shenging Ganakai Shouming Shu. CA 1,050 064 20 Mar 1991 Appl. 89 106 694 04 Sept 1989 CA 115: 2823821 (1991). The title process is described by heating black liquor with SO2 to separate lignin and recover Na sulfite from the remaining acidic solution. Treatment of black pulp liquor by conservation Zhang M; F Z; Shenging G; Shouming S. CA 1, 057 079. 18 Dec. 1991 Appl. 90, 104, 181 5 Jun 1990 CA 117:173 646 c (1992). Black pulping liquor is treated by adding solid CaCI2 or aq. Solution containing CaCIa (2-5g/100ml) to black pulping liquor, coagulating and precipitating to remove lignin and recovered diluted NaOH solution. Thus 17.5g lignin and 6g/L NaOH aqueous Solution were recovered by adding 3g CaCI2 in 100ml sulfate black liquor (from preparing of pine pulp ), precipitating and filtration. In hitherto known processes main drawbacks are as follows: 1. The use of acidic media involves corrosive problems. 2. Use of alkaline media causes further filtration problems due to colloidal particles. These processes result in incomplete removal of organics as well as inorganic matter from the effluent resulting in to coloured effluent water due to organics such as lignin and mellanoidin. The adsorbent used is commercially available chemosorbent. The following references will be useful for assessing the characters & growth pattern of red alga in general and Porphyra & Liagora in particular. Effect of effluent from sewage disposal plant on the growth of Porphyra. Ohgai, M.: Sugimoto, T; Murase, N.; Suisan, Z. 199442 (1)41-6, CA 121: 153004w(194). 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 concentrations 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 chemicals in seawater by monitoring seaweed growth are discussed. Strongest toxic substances for growth of Porphyra 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: 11034929q.(1989) Four kinds of chlorinated solutions were investigated to identify the causative substance inhibiting the growth of Porphyra yezoensis thalli. Inhibitory effects were measured in terms 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 growth inhibition of Porphyra. Utilization of nitrogen and phosphorus from treated sewage and bay sediment by marine algae. Nobuyoshi, L; Kunio, K.; Yuji, 0.; Takashi, N.; Zasshi, G.; 1987 42(1/2) CA: 108 173165j.(1988) Porphyra yzoensis preferred NH4-N to N03-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.(1995) 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 characterized by its bauxite 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 Liagora valida 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 B-1-3 linkages between D- xylopyranose residues 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. 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 black liquor produced in the paper mill wastes. 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 when the black liquor of paper mill waste is contacted with certain biological material such as marine red algae colouring matter as well organics & inorganic matter get removed from the waste water. It is noticed that when marine alga belonging to group Rhodophyceae essentially containing polysaccharides having sulfate or acetyl functional group on cell wall and galactopyranose on the membrane are used for treatment of black liquor from paper mill waste removes organics, inorganics & color significantly. In the process of the present invention, lignin organic, sugars inorganic are separated by treating the black liquor with seaweed Porphyra / Liagora and calcarious material preferably lime powder. Seaweed Porphyra is 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 the use of seaweed polysaccharide of Porphyra as a decolorizing agent is not mentioned. The combination Porphyra and calcarious material found to remove organics, inorganics and the removal of the color of spent wash from black to pale yellow, which when further treated with active carbon results in almost colorless liquid. The species of marine algae, particularly Porphyra or Liagora, has chemical structure such as 1,3 linked ß- D-galactopyranose and 1,4 - linked 3,6 -anhydrous alpha - L-galactopyranose and other charged groups like mannans and xylans on cell membrane having better phycocolloid properties and anionic polyelectrolytes with marked ion exchange properties. Further at pH > 3 sulfated polysaccharide porphyran, xylomannan, several fractions of neutral polysaccharides like D-xylopyranose, D-mannose and D-mannopyranose present on cell wall are responsible for the selective absorption of coloring chromospheres and potassium with the sorption of the lignin polyphonic bodies, the obtained pale yellow effluent treated with like 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 treatment of agro based black liquor preferably from paper mill wastes, to produce potable water. 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 sulfate or acetyl group on cell wall and galactopyranose residues on cell membrane. Yet another objective of the present invention is to provide a process which does not use acidic condition for treatment of effluents, thereby reducing the hazards of corrosion problems mentioned earlier. Accordingly the present invention provides an improved process for the treatment of agro based black liquor waste to produce potable water which comprises: contacting 1:1 to 1:5 diluted black liquor with marine red algae such as porphyra or //agora sp. in the form of dry powder for a minimum period of 30 minutes preferably under stirring, treating with conventional calcarious material such as herein described wherein the ratio of Porphyra/Liagora and calcarious material to effluent ranges from 0.5 to 2.00 for a minimum period of 30 minutes preferably under stirring, separating the coagulated material so formed from supernatant by conventional methods such as herein described, 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 embodiment a marine algae is embeded in neutral matrix or natural form containing essentially, polysaccharides having sulfate/acetyl functional group on cell wall & galactopyrandse on their cell membrane In one of the embodiments of the present invention the marine red algae used may be either Porphyra or Liagora sp. In another embodiment the black liquor may be diluted 5 times using water such as tap water mineral water, natural water, distilled water, demineralized water. In still another embodiment the contacting may be carried out for 30-120 minutes and treatment with calcarious material may be effected for 30-120 minutes. In still another embodiment the calcarious material such as CaC03, lime, bone powder, shell powder, diatomaceous earth & salts of calcium and natural source there off may be used. , The ratio of Porphyra/Liagora and calcarious 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 and inorganic matter and the treated water can be recycle to the process or let into the natural resource. The process of the invention is described herein below, with reference to the following examples, which are illustrative only and should not be construed to the limit of the scope of present invention in any manner. Example -1 20 ml of black liquor was diluted to 100 ml with water and was contacted with Porphyra dried powder 1g, under stirring for 2 hrs. followed by addition of lime powder 1.0g. The sludge separated was filtered and filtrate treated with Indion resin 20 ml at 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 get colorless water with no organic matter. Color reduction was 92%. The initial COD of black liquor was 7712.64mg/L and after Porphyra and lime treatment was brought down 1021.76mg/L and further to 12mg/L with ion exchange system ,BOD of colorless water was 26. Example -2 20 ml of black liquor was diluted to 100 ml with water and was contacted with Porphyra dried powder O.5gm. Under stirring for 2hrs. followed by addition of lime powder 0. 5 gms. 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 black liquor was 7712.64mg/L and after Porphyra and lime treatment was brought down to 1326.40mg/L and further to 60mg/L with ion exchange system ,BOD of colorless water was 20. Example -3 20ml of black liquor 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 93%. The initial COD of black liquor was 7721.64mg/L and after Porphyra and lime treatment was brought down to 2229.89mg/L and further to 88mg/L with ion exchange system, BOD of colorless water was 22. Example -4 20ml of black liquor was diluted to 100ml with water and was contacted with Liagora dried powder 1gm. under stirring for 2hrs. followed by addition of. lime powder I.Ogms. 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 black liquor was 7712.64mg/L and after Liagora and lime treatment was brought down to 995.4mg/L and further to 12mg/L with ion exchange system ,BOD of colorless water was 26. Example -5 20ml of black liquor was diluted to 100ml with water and was contacted with Liagora dried powder O.Sgm. 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 carbon 5g. to colorless water with no organic matter. Color reduction was 94%. The initial COD of black liquor was 7712.64mg/L and after Liagora and Lime treatment was brought down to 1033.4mg/L and further to 60mg/L with ion exchange system , 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 carbon5g. to colorless water with no organic matter. Color reduction was 97%. The initial COD of spent wash was 7712.64mg/L and after Liagora and lime treatment was brought down to 2021.76mg/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 claim: 1. An improved process for the treatment of agro-based black liquor waste to produce potable water which comprises : contacting the 1:1 to 1:5 diluted black liquor with marine red algae selected from group Porphyra or Liagora sp. in the form of dry powder for a period ranging from 30 to 120 minutes preferably under stirring, treating with conventional calcarious materials such as herein described wherein the ratio of Porphyra I Liagora and calcarious material to effluent ranges from 0.5 to 2.0 for a period ranging from 30 to 120 minutes preferably under stirring, separating the coagulated material so formed from supernatant by conventional methods such as herein described, and optionally treating the 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 calcarious material used is selected from lime, bone powder, shell powder, diatomaceous earth, salts of calcium and natural source thereof. 3. An improved process as claimed in claims 1 to 2, wherein the black liquor is diluted using tap water, mineral water, natural water, demineralized water or distilled water. 4. An improved process as claimed in claims 1 to 3, wherein the separation of coagulated material is carried out by conventional sedimentation, filtration, centrifugation under conditions such as herein described. 5. An improved process for the treatment of agro-based black liquor waste to produce potable water substantially as described herein before with reference to the examples.

Full Text

This invention relates to an improved process for the treatment of Agro based black liquor waste to produce potable water. More particularly the invention relates to an improved process for treatment of black liquors from paper mills by removing organic and inorganic matter, lignin and coloring matter using marine biological material.
Lignin may be defined as amorphous polyphenolic material arising from an enzyme mediated dehydrogenative polymerization of three phenylpropanoid monomers, of e.g. conyferyl, sinapyl and p-coumaryl alcohols.
Lignin (from the Latin lignum, wood) after cellulose is the principal
constituent of woody structure of higher plants in part deposited in xylem cell walls, in part located in the intercellular spaces.
The sulfite waste liquors from paper mills contain upto 3 to 6% lignin, which are not easily biodegradable. This lignin may act as a source of vanillin, syringic aldehyde, can be used as extender for phenolic plastics as well as to strengthen the rubber, as oil mud additive to stabilize asphalt, as emulsions to precipitate proteins.
Lignin also can be converted to pure low molecular weight chemicals; it may serve as an important feedstock for the chemical industry. At present only vanillin and dimethyl sulfide are produced commercially and economically, However, competitive processes for conversion of lignin to phenolic and aromatic
chemicals are real possibilities.
Until the past 2-3 decades or so, large amounts of
lignin were discarded into streams and waterways as dilute aqueous solutions which is not tolerated now and almost all waste streams containing lignin are

concentrated and burned.
The process of the present invention is environment friendly & convert hazardous waste to a potable water and helps in preserving environment as per environmental pollution act.
In order to conform to environmental quality guidelines, a number primary and secondary treatment systems to control effluents are installed; treatment comprises clarifires to remove 85-1 OOwt. % of solid such as clarifires in first treatment and lagoons aerated or otherwise, trickling filters, modified biological systems, charcoal treatment etc. to remove as 90-95% of BOD, most solid, most of the toxicity except very little color.
Ultrafiltrations also has been tried and found futile to remove total dissolved solids completely.
The pulp and paper industry uses large amounts of water which is recycled and reused resulting in temperature rise and dissolution of more solids in water enhancing problems e.g. corrosion, slime and other deposits. Directly or indirectly all of these viz. BOD, color and toxicity may effect aquatic life.
Total dissolved solids are removed and used as energy source in fuel. Biomethanation has also been attempted. All these do not meet the standards of pollution control. Therefore it becomes very essential to remove color, total dissolved solids with negligible quantity of BOD and COD.
In the prior art following methods are used for the separation of lignin from black liquor in paper industry. Several methods hitherto used are described in brief herein bellow:

Purification of waste waters for installation of bleaching sulfate paper
Udeleholms A.B. Fr. Demande 2, 202,043 03 May 1974. Swed Appl. 12772/72 04 Oct. CA 82: 34833 g (1975).
The lignin and other organic matter are mostly precipitated from wastewater by addition of mineral acid and by filtration. The filtered wastewater is treated with feebly alkaline ion exchange resin activated with acid and then resin is eluted with alkali to remove adsorbed lignin. The elute together with solution of original precipitate in alkali are recycled to the sulfate pulp process, preferably by burning in the black liquor recovery process. In this process the ion exchange resins used are commercially available chemical components.
Desulfurisation of waste gas with pulp waste liquor Suyama A; Hayashi, H (Mitsubishi Kausha Ltd. Toyo Tokushi Kogyo K. K.) Jap. Kokai 76,20,089 17 Feb. 1976. CA 85: 67527a 9(1976). Fiber free black
liquor is used for waste gas desulfurisation and lignin in waste liquor is
precipitated as lignin sulfate. The fiber is removed by boiling. Thus 1100 ppm
S02 containing diesel oil boiler flue gas was desulfurised with boiled black
liquor (pH 12) to desulfurise 93%. The spent liquor was air oxidized and
coagulant was added to precipitate lignin and others.
Recovery of sodium hydroxide and black liquor from cellulose
manufacture
Torras hostench S. A. Belg. 861, 585 31 March 1977. Span Appl. 461, 364 04
Aug. 1977. CA 89: 61292 (1978).
An improved process for title recovery as compared to Spanish patent
No. 29, 158 comprises carbonation of spent liquor (preconcentrated to 40%

from 10-15%) from treatment of pulp by bubbling C02 through a stream of spent liquor in a counter current system from bottom to the top of the liquor at 75-85 and 0.5kg/cm2 and treating the resulting silica -lignin precipitate with 0.03 N NaOH to redissolve the lignin for recycling to carbonated black liquor before further concentrating by evaporating.
Recovery of inorganic compounds from Kraft pulping black liquors Domtar Inc. Jpn. Kokai Tokkyo Koho 58 36292 (83 36292) 03 Marc. 1985. Appl.382387 23 July 1981. CA 99: 89814 h (1983).
Sodium compound from Kraft pulping black liquors are recovered by
first acidifying the cool liquor with acids containing HaS04 to Kraft black liquor by ultracentrifugation (DC) of liquor, followed by electrodialysis (E) of UC
permeate, treating deionate from electrodialysis with acid to precipitate lignin and electrolytic H20 splitting of resulting solution.
Removal of lignin alkaline waste pulping liquors
Ishikawa H.; Kade K. (Oji Paper Co. Ltd.). Jpn. Kokai Tokkyo JP 62 90398 (87 90 389) 24th April 1987 85 226 870 Oct. 1985. CA 107: 79 808 d (1987).
The title removal involved colloidising the solution lignin followed by ultrafiltration. Thus beech chips were cooked at effective alkali 14% sulfidity 25%, liquor ratio 4 and 165. The resulting black liquor was filtered, adjusted to pH 11,10 and 9 with which CO2and ultra filtered to give delignification 89%, 94% and 97% respectively.
Manufacture of methylolated lignin from black Kraft liquor residues Diliing Peter (West Vaco Corp.) US 4, 764,59716 Aug. 1988 Appl. 61 460 15 Jun 1987 CA 109: 212612v (1988).
Methylolated lignin is manufactured from black Kraft liquor residues by

initially oxidizing black Kraft liquor containing lignin and salt in situ methylolation of lignin with an aldehyde followed by lowering the pH of the black Kraft liquor residue to precipitate methylolated lignin and finally recovering the precipitated methylolated lignin from black liquor residue. Thus a black Kraft residue (pH 13) was oxidized with air until the Na2S content was 1% and then stirred with 31b/mole HCHO/1000 Ib lignin at 70 for 2h. The black liquor containing methylolated lignin was acidified with HaS04 to pH4. The methylolated lignin was coagulated, filtered, washed with water. The methylolated slurry was then treated with triethanolamine to pH7 and then sulfonated with S02 at 205°F for 12h to give sulfomethylolated amine salt useful as dispersent for azodyes. Recovery of solids from black liquors
Caperos, S.A. Span ES 2, 006, 964 16 May 1989 Appl. 8, 801,697 27 May 1988. CA 114: 26042 n (1991).
Solids in black liquors are recovered, as precipitate by mixing 1 part black liquor with 0.1-1.0 parts reactive precipitating agent and separating the precipitate. The black liquor electrodialysed globules was mixed with equal volume of saturated solution of CaCI2 in EtOH to form precipitate which was separated with centrifuged and washed with 1:1 EtOH- water to give precipitate 134 parts, organic components 105 parts, lignin 53 parts and pentosans 8g with 85% yield.
Areding process of paper black liquor with sulfur-dioxide
Sun, L; Xu, Mu, H et al (Chinese Academy of Sciences, environment-estimating department). Faming Zhuangli Shenging Ganakai Shouming Shu. CA 1,050 064 20 Mar 1991 Appl. 89 106 694 04 Sept 1989 CA 115: 2823821 (1991).

The title process is described by heating black liquor with SO2 to separate lignin and recover Na sulfite from the remaining acidic solution.
Treatment of black pulp liquor by conservation
Zhang M; F Z; Shenging G; Shouming S. CA 1, 057 079. 18 Dec. 1991 Appl. 90, 104, 181 5 Jun 1990 CA 117:173 646 c (1992).
Black pulping liquor is treated by adding solid CaCI2 or aq. Solution containing CaCIa (2-5g/100ml) to black pulping liquor, coagulating and precipitating to remove lignin and recovered diluted NaOH solution. Thus 17.5g lignin and 6g/L NaOH aqueous Solution were recovered by adding 3g CaCI2 in 100ml sulfate black liquor (from preparing of pine pulp ), precipitating and filtration.
In hitherto known processes main drawbacks are as follows:
1. The use of acidic media involves corrosive problems.
2. Use of alkaline media causes further filtration problems due to colloidal
particles. These processes result in incomplete removal of organics as well as
inorganic matter from the effluent resulting in to coloured effluent water due to
organics such as lignin and mellanoidin.
The adsorbent used is commercially available chemosorbent.
The following references will be useful for assessing the characters & growth
pattern of red alga in general and Porphyra & Liagora in particular.
Effect of effluent from sewage disposal plant on the growth of Porphyra.
Ohgai, M.: Sugimoto, T; Murase, N.; Suisan, Z. 199442 (1)41-6, CA 121: 153004w(194).
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 concentrations 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
chemicals in seawater by monitoring seaweed growth are discussed. Strongest
toxic substances for growth of Porphyra 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:
11034929q.(1989)
Four kinds of chlorinated solutions were investigated to identify the causative substance inhibiting the growth of Porphyra yezoensis thalli. Inhibitory effects were measured in terms 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 growth inhibition of Porphyra.
Utilization of nitrogen and phosphorus from treated sewage and bay sediment by marine algae.
Nobuyoshi, L; Kunio, K.; Yuji, 0.; Takashi, N.; Zasshi, G.; 1987 42(1/2) CA: 108 173165j.(1988)

Porphyra yzoensis preferred NH4-N to N03-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.(1995) 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 characterized by its bauxite 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 Liagora valida 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 B-1-3 linkages between D- xylopyranose residues 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.
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 black liquor produced in the paper mill wastes. 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 when the black liquor of paper mill waste is contacted with certain biological material such as marine red algae colouring matter as well organics & inorganic matter get removed from the waste water.
It is noticed that when marine alga belonging to group Rhodophyceae essentially containing polysaccharides having sulfate or acetyl functional group on cell wall and galactopyranose on the membrane are used for treatment of black liquor from paper mill waste removes organics, inorganics & color significantly.
In the process of the present invention, lignin organic, sugars inorganic are separated by treating the black liquor with seaweed Porphyra / Liagora and calcarious material preferably lime powder. Seaweed Porphyra is 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 the use of seaweed polysaccharide of Porphyra as a decolorizing agent is not mentioned. The combination Porphyra and calcarious material found to remove organics, inorganics and the removal of the color of spent wash from black to pale yellow, which when further treated with active carbon results in almost colorless liquid.

The species of marine algae, particularly Porphyra or Liagora, has chemical structure such as 1,3 linked ß- D-galactopyranose and 1,4 - linked 3,6 -anhydrous alpha - L-galactopyranose and other charged groups like mannans and xylans on cell membrane having better phycocolloid properties and anionic polyelectrolytes with marked ion exchange properties.
Further at pH > 3 sulfated polysaccharide porphyran, xylomannan, several fractions of neutral polysaccharides like D-xylopyranose, D-mannose and D-mannopyranose present on cell wall are responsible for the selective absorption of coloring chromospheres and potassium with the sorption of the lignin polyphonic bodies, the obtained pale yellow effluent treated with like 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 treatment of agro based black liquor preferably from paper mill wastes, to produce potable water. 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 sulfate or acetyl group on cell wall and galactopyranose residues on cell membrane.
Yet another objective of the present invention is to provide a process which does not use acidic condition for treatment of effluents, thereby reducing the hazards of corrosion problems mentioned earlier.
Accordingly the present invention provides an improved process for the treatment of agro based black liquor waste to produce potable water which comprises: contacting 1:1 to 1:5 diluted black liquor with marine red algae

such as porphyra or //agora sp. in the form of dry powder for a minimum period of 30 minutes preferably under stirring, treating with conventional calcarious material such as herein described wherein the ratio of Porphyra/Liagora and calcarious material to effluent ranges from 0.5 to 2.00 for a minimum period of 30 minutes preferably under stirring, separating the coagulated material so formed from supernatant by conventional methods such as herein described, 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 embodiment a marine algae is embeded in neutral matrix or natural form containing essentially, polysaccharides having sulfate/acetyl functional group on cell wall & galactopyrandse on their cell membrane
In one of the embodiments of the present invention the marine red algae used may be either Porphyra or Liagora sp.
In another embodiment the black liquor may be diluted 5 times using water such as tap water mineral water, natural water, distilled water, demineralized water.
In still another embodiment the contacting may be carried out for 30-120
minutes and treatment with calcarious material may be effected for 30-120 minutes. In still another embodiment the calcarious material such as CaC03, lime,
bone powder, shell powder, diatomaceous earth & salts of calcium and natural source there off may be used.
, The ratio of Porphyra/Liagora and calcarious 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 and inorganic matter and the treated water can be recycle to the process or let into the natural resource.
The process of the invention is described herein below, with reference to the following examples, which are illustrative only and should not be construed to the limit of the scope of present invention in any manner.
Example -1
20 ml of black liquor was diluted to 100 ml with water and was contacted with Porphyra dried powder 1g, under stirring for 2 hrs. followed by addition of lime powder 1.0g. The sludge separated was filtered and filtrate treated with Indion resin 20 ml at 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 get colorless water with no organic matter. Color reduction was 92%. The initial COD of black liquor was 7712.64mg/L and after Porphyra and lime treatment was brought down 1021.76mg/L and further to 12mg/L with ion exchange system ,BOD of colorless water was 26.

Example -2
20 ml of black liquor was diluted to 100 ml with water and was contacted with Porphyra dried powder O.5gm. Under stirring for 2hrs. followed by addition of lime powder 0. 5 gms. 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 black liquor was 7712.64mg/L and after Porphyra and lime treatment was brought down to 1326.40mg/L and further to 60mg/L with ion exchange system ,BOD of colorless water was 20.
Example -3
20ml of black liquor 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 93%. The initial COD of black liquor was 7721.64mg/L and after Porphyra and lime treatment was brought down to 2229.89mg/L and further to 88mg/L with ion exchange system, BOD of colorless water was 22.
Example -4
20ml of black liquor was diluted to 100ml with water and was contacted with Liagora dried powder 1gm. under stirring for 2hrs. followed by addition of. lime powder I.Ogms. 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 black liquor was 7712.64mg/L and after Liagora and lime treatment was brought down to 995.4mg/L and further to 12mg/L with ion exchange system ,BOD of colorless water was 26.
Example -5
20ml of black liquor was diluted to 100ml with water and was contacted with Liagora dried powder O.Sgm. 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 carbon 5g. to colorless water with no organic matter. Color reduction was 94%. The initial COD of black liquor was 7712.64mg/L and after Liagora and Lime treatment was brought down to 1033.4mg/L and further to 60mg/L with ion exchange system , 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 carbon5g. to colorless water with no organic matter. Color reduction was 97%. The initial COD of spent wash was 7712.64mg/L and after Liagora and lime treatment was brought down to 2021.76mg/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 claim:
1. An improved process for the treatment of agro-based black liquor waste
to produce potable water which comprises : contacting the 1:1 to 1:5
diluted black liquor with marine red algae selected from group Porphyra
or Liagora sp. in the form of dry powder for a period ranging from 30
to 120 minutes preferably under stirring, treating with conventional
calcarious materials such as herein described wherein the ratio of
Porphyra I Liagora and calcarious material to effluent ranges from 0.5 to
2.0 for a period ranging from 30 to 120 minutes preferably under stirring,
separating the coagulated material so formed from supernatant by
conventional methods such as herein described, and optionally treating
the 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 calcarious material
used is selected from lime, bone powder, shell powder, diatomaceous earth, salts of calcium and natural source thereof.
3. An improved process as claimed in claims 1 to 2, wherein the black liquor
is diluted using tap water, mineral water, natural water, demineralized water or distilled water.
4. An improved process as claimed in claims 1 to 3, wherein the separation
of coagulated material is carried out by conventional sedimentation,
filtration, centrifugation under conditions such as herein described.
5. An improved process for the treatment of agro-based black liquor waste
to produce potable water substantially as described herein before with
reference to the examples.

Documents:

1085-del-1999-abstract.pdf

1085-del-1999-claims.pdf

1085-del-1999-correspondence-others.pdf

1085-del-1999-correspondence-po.pdf

1085-del-1999-description (complete).pdf

1085-del-1999-form-1.pdf

1085-del-1999-form-19.pdf

1085-del-1999-form-2.pdf

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Patent Number

216746

Indian Patent Application Number

1085/DEL/1999

PG Journal Number

13/2008

Publication Date

31-Mar-2008

Grant Date

19-Mar-2008

Date of Filing

10-Aug-1999

Name of Patentee

COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH

Applicant Address

RAFI MARG, NEW DELHI-110001, INDIA.

Inventors:

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

PCT International Classification Number

C02F 3/32

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA