|Title of Invention||
AN IMPROVED PROCESS FOR THE TREATMENT TO BALCK LIQUOR WASTE USING MARINE SPONGE TO PRODUCE POTABLE WATER .
|Abstract||The invention provides an improved process for the treatment of black liquor waste using marine sponge to produce potable water. Marine sponge particularly from phylum porifera class Demospongia such as Mycale mytilorum, Acctenella forminifera, Presteylessa foetida, Sygmadoin carnosa & Callyspongia fibrosa is used for the treatment of black liquor waste.|
|Full Text||This invention relates to an improved process for the treatment of black liquor waste using marine sponge to produce potable water. More particularly it relates to separation of lignin & colouring matter from black liquor waste through adsorption technology. Marine sponge particularly from Phyllum Porifera class Demospongia such as Mycale mytilorum, Acctenella forminifera, Presteylessa foetida, Sygmadoin carnosa & Callyspongia fibrosa can be used for the treatment of black liquor waste.
Accordingly to the widely accepted concept lignin may be defined as amorphous plyphenolic material arising from an enzyme mediated dehydrogenate polymerization of three phenylpropanoid monomers, of e.g. conyferyl, sinapyl and p-coumaryl acohols.
Lignin (from the Latin lignin, wood) is after cellulose, 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 is 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 is produced commercially and economically competitive processes for conversion to phenolic and aromatic chemicalsare 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 of 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 below:
Purification of waste waters from installations for 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 91976).
Fiber free black liquor is used for waste gas desulfurisation and lignin in waste liquor is precipitated as lignin sulfate. The fibre is removed by boiling. Thus 1100 ppm SO2 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 Co2 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 liquor 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 H2SO4 to Kraft black liquor by ultracentrifugation (UC) of liquor, followed by electrodialysis (E) of UC permeate treating deionate from E with acid to precipitate lignin and electrolytic H2O 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% sufidity 25% liquor ratio 4 and 165. The resulting black liquor was filtered, adjusted to pH 11, 10 and9 with which CO2 and ultra filtered to give delignification 89%, 94% and 97% respectively.
Manufacture of methylolated lignin from black kraft liquor residues Dilling Peter (West Vaco Corp.) US 4, 764,59716 Aug. 1988 Appl. 61 460 15 Jun 1987 CA 109: 212612 v (1988).
Methylolated lignin (I) is manufactured from black Kraft liquor residues by initially oxidizing black Kraft liquor containing (I) and salt in situ methylolation of (I) with an aldehyde followed by lowering the pH of the black Kraft liquor residue to precipitate methylolated (I) and finally recovering the precipitated methylolated (I) 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 I at 70 for 2h. The black liquor containing methylolated I was acidified with H2SO4 to pH4. The methylolated I was coagulated at 85, filtered, washed with water. The methylolated slurry was then treated with triethanolamine to pH7 and then sufonated with SO2 at 205F for 12h to give sulfomethylolated. I amine salt useful as dispersing 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 agents and separating the precipitate. The 1000cm2 black hquor E globules was mixed with 1000cm2 saturated of solution of CaCI2 in EtOH to form precipitate which was separated with centrifuge and washed with 1:1 EtOH- water to give ppt. 134, organic components 105 lignin 53 and pentosans 8g with 85% yield. Arending process of paper black liquor with sulfue-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: 282382 t
The title process is described by heating black liquor with SO2 to separate lignin and recover Na sulfite from the remaining acidic solution. Treatement of black pulp liquor by conservation and precipitation 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 CaCl2 (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 aq. Solution were recovered by adding 3g CaCI2 in 1ooml sulfate black liquor (from preparing of pine pulp), precipitating and filtration.
Materials for removing hazardous ions from waters Atsukari, Y.; Takahashi, Y.; 1993 CA: 260631 h.
The protein fiber material for removing hazardous ions (e.g. free chlorine) from waters comprise alternately staked layers of 1. dual layer comprising wool and activated carbon and 2. dual layer comprising wool and sponge.
Separation and enrichment of trace silver with sponges Zhou, Z.; Chen, W.; Guijinshu 1991 12(4) CA: 30961 r.
A method for separation and enrichment of trace Ag with sponge was studied. Adsorption selectivity and cone, effect for complex of Ag and 1,10-phenanthroline are geod. In the presence of EDTA, the other metal ions cannot be adsorbed. AgPb can be eluted quant, by 1M HNO3 for 96.3 adsorbed.
Waste water treatment plant with Bioexcel and HCF systems
Tsukui, R.; Ito, H.; Ebara, Z.; 1996 CA: 22467e.
Wastewater treatment plant equipped with a Bioexcel system (a biotreatment system featuring filtration by sponge filter media and a HVF system. The BOD, COD and SS in the raw wastewater were 950,680 and 300 mg/L and the treated wastewater were 140,160 and 50mg/l. Utilization of a sponge media integrated fixed film activated sludge process for treatment of high ammonia industrial wastewater Louis, R.; Randall, C. 1995 CA: 324364g.
Process characteristics of an integrated fixed film activated sludge treatment system utilizing the sponge media LINPOR were investigated for treatment of a high strength, high ammonia N - industrial wastewater. Operating bench scale anoxic aerobic reactor of media cone. 10,20,30 and 40 performed the evaluations.
In the process of the present lignin organics, sugars, inorganics separated by treating the black liquor with marine sponge and seashell powder.
The inventors of the present invention are reporting the use of marine sponge as a decoloring agent for the first time and no references to that effect are available in literature. The combination of sponge and naturally occuring calciferous material such as muscle shells, sea shells, bone mill preferably oyster shell powder found to remove organics, inorganics and the removal of the color of the black liquor from black to pale yellow, which further treated with active carbon to get almost colorless liquid. 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.
In hitherto known processes main drawback are as follows:
The use of acidic media involves corrosive problems. The use of alkaline media causes further filtration problems due to colloidal particles and results in to incomplete removal of organic as well as inorganic matter from the effluent resulting in to colored effluent water due to organic mainly lignin and mellanoidin.
The adsorbant media used is commercially available chemosorbents.
There is continued interest on development of new improved processes for separation of lignin organic matters; inorganic compounds from black liquor produced in paper mill wastes. It is he known fact those lignin-containing effluents are not degradable and hence has disposal problems in the environment.
In the present invention marine sponqe is employed as a decoloring agent for the first time and no references to that effect are available in the literature. The combination of sponge and pretreated naturally occurring Calciferous material preferably oyster shell powder found to remove organics, inorganics and color of the black liquor from black to pale yellqw, which further treated with active carbon to get almost colorless liquid.
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.
The invention is based on our finding that in the presence of Sponge, chemical constituents like highly sulfated groups rich in N-acetylglucoseamine, N-acetylgalactoseamine, glucuronic acid along with amino sugars having better phycocolloid properties and anionic polyelectrolytes with marked cation exchange properties must be of some significance in marine fauna & can be used effectively to remove pollutants form the waste.
Further at pH >3 sulfated groups and several fractions of neutral polysaccharides like N-acetylglucose amine, N-acetylgalactoseamine are responsible for the selective absorption of coloring chromophores and potassium with the adsorption of the lignin polyphenolic bodies, the obtained pale yellow effluent treated with Lime power CaO > 98%, ion exchange system and activated carbon to remove organic, inorganic 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 black liquor using marine sponge to produce potable water by separation of coloring matter, inorganic matter and lignin from black liquor produced in the paper mill waste industries. The water produced meets all environmental standards for treated effluents.
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 and other problems mentioned earlier.
Accordingly the present invention provides an improved process for the treatment of black liquor waste using marine sponge to produce potable water which comprises contacting marine sponge powder and black liquor ( diluted 1:1 to 1:5) for a period ranging 5 minutes to 2 hr, under stirring, adding naturally occurring calciferous material such as herein described , and maintaining at a pH 7.0 for 30 minutes , separating the supernatant from the sludge so formed by conventional methods , treating the resultant with ion exchange resin followed by activated charcoal to get colourless potable water.
In one of the embodiment of the present invention the black liquor used may be diluted 1:5 times using tap water, demineralised water, distilled water, natural potable water.
In the embodiment of the present invention the amount of Sponge & natural calciferous material may be 1.0% w/v of black liquor.
In another embodiment of the present invention the marine sponge used may be any marine sponge preferably belonging to Phyllum porifera class Demospongia more preferably such as Myxilla arenaria, Mycale Mytilomium, acctenella forminifera, Presteylessa foetida.
In still another embodiment of the present invention the marine sponge used may be collected from mandapam gulf of Mannar & Malvan Gulf of Kuctchh deposited at NIO has accession no. NIO-WD/1940/1007 and characteristics as given below.
1. Primitive, multicellular animal
2. Internal skeleton of spicules made up of calcium carbonate, silicic acid and
3. Lacks nervous system and sensory cells
4. Large osculum and many ostra with transport canals.
5. Various shapes and sizes.
6. Sessile forms
7. Asexual reproduction by gemmules and sexual reproduction by eggs and
8. Encrusting small cushion like or braanched forms characterised by
acanthostyles spicules consisting of bundles inside the sponge.
9. Tornotes arranged at a fatment to the surface isachorus or osochelas and
10. Body pad like lumpy, surface uneven.
11 .Colouration greyish white or yellow and light brown.
Further the selected sponge may be having α-amino acids (e.g. serine), D-glucuronic acid N-acetyl-α-D-galactose amine functional groups on cell wall.
Sponge may be made available to public for research after observing normal set procedures.
The sponge used may be such as dehydrated one in a powder form embedded on inert matrix and the amount of sponge added may be preferably between 0.25 gm - 1.0 gm / 100ml of diluted waste.
In still another embodiment of the present invention the calciferous material used may be oyster shell powder, seashell, muscle shell powder.
The calciferous material preferably may be activated by heating at 800°C for 4-6 hours. The separation of supernatant from sludge may be
carried out by filtration, sedimentation and centrifugation.
In another embodiment of the present invention the ion exchange resin is selected from anion/ cation exchanger resin from loba Chemic under brand name IR-120, IR-400 and Indion from Ion Exchange India.
In the feature of the present invention the treated black liquor wash was found to be passing COD/BOD and all other parameters of effluent agencies.
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 inorganic and the treated water can be recycled to the process.
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 black liquor was diluted to 100ml with water and was treated with Sponge dried powder 1gm. under stirring for 2hrs. followed by addition of oyster shell powder 1.0gm. 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 97%. The initial COD of black liquor was 67883.2mg/L and after Sponge and oyster shell treatment was brought down to 5180.2mg/L and further to
12mg/L with ion exchange system and BOD of colorless water was 26. Example -2
20ml of black liquor was diluted to 100ml with water and was treated with Sponge dried powder 0.5gm. under stirring for 2hrs. followed by addition of activated oyster shell powder 0.5gm
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 92 %. The initial COD of black liquor was 67883.2mg/L and after Sponge and Oyster treatment was brought down to 5997.2mg/L and further to 60mg/L with ion exchange system and BOD of colorless water were 20. Example -3
20ml of black liquor was diluted to 100ml with water and was treated with Sponge dried powder 0.25gm. under stirring for 2hrs. followed by addition of activated oyster shell 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 88%. The initial COD of black liquor was 69873.1mg/L and after Sponge treatment was brought down to 5432.9mg/L and further to 88mg/L with ion exchange system and BOD of colorless water were 22. 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.
1. An improved process for the treatment of black liquor waste
using marine sponge to produce potable water which comprises
contacting marine sponge powder and black liquor ( diluted 1:1
to 1:5) for a period ranging 5 minutes to 2 hr, under stirring,
adding naturally occurring calciferous material such as herein
described , and maintaining at a pH 7.0 for 30 minutes ,
separating the supernatant from the sludge so formed by
conventional methods , treating the resultant with ion exchange
resin followed by activated charcoal to get colourless potable
2. An improved process as claimed in claim 1, wherein the black
liquor used is diluted by agent selected from tap water,
demineralised water, distilled water, natural potable water.
3. An improved process as claimed in claims 1 & 2, wherein the
calciferous material used is selected from oyster shell powder,
sea shell, muscle shell powder.
4. An improved process as claimed in claims 1 to 3 , wherein the
calciferous material used is activated by heating at 800°C for 4
- 6 hours.
5. An improved process as claimed in claims 1 to 4, wherein the
amount of Sponge & natural calciferous material is 1.0% w/v of
black liquor waste.
6. An improved process as claimed in claims 1 to 5, wherein the
marine sponge used is selected from phylum Porifera class
Demospongia , preferably such as Myxilla arenaria, Mycale
mytilomium, Acctenella forminifera, Presteylessa foetida.
7. An improved process as claimed in claims 1 to 6, wherein the
marine sponge used is selected from dehydrated powder
embedded on inert matrix and the amount of sponge added is
preferably between 0.25 gm - 1.0 gm / 100ml of diluted waste.
8. An improved process as claimed in claims 1 to 7, the separation
of supernatant from sludge is carried out by filtration,
sedimentation and centrifugation.
9. An improved process as claimed in claims 1 to 8, wherein the
ion exchange resin is selected from anion/cation exchanger
10. An improved process for the treatment of black liquor waste using marine sponge to produce potable water substantially as herein described with reference to the examples.
|Indian Patent Application Number||1447/DEL/1999|
|PG Journal Number||40/2007|
|Date of Filing||05-Nov-1999|
|Name of Patentee||COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH|
|Applicant Address||RAFI MARG, NEW DELHI-110 001. INDIA|
|PCT International Classification Number||C02F 3/32|
|PCT International Application Number||N/A|
|PCT International Filing date|