Title of Invention

A METHOD OF MAKING A COMPOSITION FOR SELECTIVELY ABSORBING OIL FROM A MIXTURE CONTAINING SUCH OIL

Abstract

A method of making a composition for selectively absorbing oil from a mixture containing such oil, consisting of dusting of cleansed cotton fibres by loose beating of two types, Type A having staple length of 12 to 20 mm, a trash of 20 per cent, micronaire value of 2.5 to 4.5 and a Gm/Tex ranging from 9-14 and Type B having staple length of 21 to 23 mm, a trash of 12 to 15 per cent, micronaire value of 3.5 to 5 and a Gm/Tex ranging from 12-20 in the ratio of Type A to Type B of approximately 1: 1; injecting a micro-organisms which is mesophilic, celluloytic and hydrophobic in nature into the mass of said dusted cotton fibres; drying the said mass of cotton fibres at temperatures ranging from 25 to 35 degrees C; homogenising and fluffing the dried fibres to obtain an oil absorbing mass having a density of 0.4-0.8.

Full Text

FORM-2 THE PATENTS ACT, 1970 (39 of 1970) COMPLETE (Section-10, rule 13} A METHOD OF MAKING A COMPOSITION FOR SELECTIVELY ABSORBING OIL FROM A MIXTURE CONTAINING SUCH OIL (a) RADHA GOPALAN of B/302, Birchwood, Hiranandani Gardens, Powai, Mumbai 400 076, Maharashtra, India; (b) SHANTARAM MALEY of 21/C, Navalgarkul Hsg. Society, Siddharth Nagar, Vakola, Santacruz (E), Mumbai 400 076, Maharashtra, India; and (c) IRFAN FURNITUREWALA of 62, Peridot, Perry Cross Road, Bandra(W), Mumbai 400 050, MaharashtraT India, all Indian Nationals THE FOLLOWING SPECIFICATION PARTICULARLY DESCRIBES THE NATURE OF THIS INVENTION AND THE MANNER IN WHICH IT IS TO BE PERFORMED:- The invention relates to a method of making novel bio-absorbent composition and to articles made therefrom. Particularly, this invention relates to an ecofriendly product useful in managing oil spills. In the 70's solvent - emulsifiers were used in oil spills with the idea that tidal volume and strong currents will emulsify oil rapidly and it will get mixed, dispersed and flushed out. Dispensing and cleansing the shore was a Major hurdle. So mechanical methods were sought. Traditionally spill - booms were used which is but baulks of timber but was quickly changed to buoyant tubes at the end of which hung a weighted skirt. This was not flexible at oil - jetties an other alterations with multiple mooring points also had its own limitation. Another approach was 'bubble barrier' - pneumatic boom. These were ineffective against wind and broken up by waves. High capacity pumps with flexible floating hoses and flattened nozzles failed to draw off the surface film. Absorption in some porous but water repellant material like oleophilic polyurethane foams in the form of broom and mattress of 10 ft. length do absorb about 225 Ltrs. Of oil but is very expensive and is not degradable. Therefore it is not environment friendly. Nitrogen and phosphorous based absorbents in petroleum degradation have been established. But the rapid dissolution of salts have little or no effect specially when applied in the sea or water - oil mixtures, (atlas RM &R.Bortha 1972) Pritchand and co workers (1973) using chemo stats have studied the biodegradation of refined oils cell-surface hydrophobicity has been reported by Marshall (1976) as an important factor in adhesion to solid surface. Other conventional products involve the use of mineral absorbents containing silicates and diatomaceous earth, clay, saw dust, cotton mops, paper products and agricultural biomass have been used in absorbing oil. But the absorption or the absorption ratio does not exceed 1:1 which creates further degradation problems. All of these have several limitations such as rate of absorption and the retention and retrieval of the oil is low. Besides, there are operational inconveniences. For example use of silica over a period of time results in silicosis of the lungs. This invention envisages the use of cotton fibres having the ability to create capsule like cavity because of it's expandable nature for enabling the entrapment of lipophillic and hydrophobic substances. The product exhibit high absorption property of oil both in aqueous / oil mixtures or oil/solid mixtures. The composition of this invention has porosity and swelling properties with cavity formation for trapping oil. The invention therefore provides a new bio-absorbent material which is useful to clean-up marine oil spills, oil well blow outs, refineries and other oil processing facilities and discharge of waste oil from industrial and municipal sources. The biosorbent is a blend of different grades of cellulosic fibres having high cell surface and hydrophobicity. It is adapted to co-agulate the spreading of oil and keep it holding. The absorbent material in accordance with this invention is porous and encapsulates oil and prevents leaching. The product is totally biodegradable. An object of this invention is to provide a method of absorbing, retrieving, remediating oil from oil - water mix/oil-solid mix and prevent the dispersion or sinking of oil with instant remediation and finally degrading it completely. According to this invention there is provided a method of making a composition for selectively absorbing oil from a mixture containing such oil, consisting of dusting of cleansed cotton fibres by loose beating of two types, Type A having staple length of 12 to 20 mm, a trash of 20 per cent, micronaire value of 2.5 to 4.5 and a Gm/Tex ranging from 9-14 and Type B having staple length of 21 to 23 mm, a trash of 12 to 15 per cent, micronaire value of 3.5 to 5 and a Gm/Tex ranging from 12-20 in the ratio of Type A to Type B of approximately 1:1; injecting micro-organisms which are mesophilic, cellulytic and hydrophobic in nature into the mass of said dusted cotton fibres; drying the said mass of cotton fibres with impregnated micro-organisms at temperatures ranging from 25 to 35 degrees C; homogenising and fluffing the dried fibres to obtain an oil absorbing mass having a density of 0.4-0.8. In accordance with a preferred embodiment of the invention the oil absorbing mass of homogenized dried fibres are enclosed in a net of desired shape and size. Typically, dusting is achieved by loose beating the fibres in a vertical cylinder that houses a shaft with four rotating pegs. Typically, the micro-organisms selected are grown in a carbohydrate rich media. Typically the fibres are dried in a loose circulatory rotary beating device Typically the dried fibres are homogenized in a rotating tumble dryer. Alternatively the dried fibres are homogenized in low temperature fluidised bed. Typically the micro-organisms are at least one mirco-organism selected from a group containing Yeasts, Pseudomonas, Escherichia, Arthrobacter, Mycobacterium, Desulfotomaculum aerobic bacteria and fungus. The composition of this invention can be used directly on an oil spill by spreading or spraying. The oil can be petrol, diesel, kerosene, vegetable oil and silicon oil or oil with high viscosity, medium viscosity and low viscosity. One advantage of this composition is that a large quantity of oil can be absorbed effectively with small volume of the absorbent (upto 15 oil :1 absorbent). The porous nature of the bio-absorbent, when floated in an oil/water mixture is able to hold viscous oil in the ratio of 1:11 to 1:15. The rate of absorption of oil when the product is spread is immediate. The composition of this invention absorbs oil from marine oil spills, refineries, land surface, industrial premises and municipal disposals and at the same time is non-toxic, eco friendly and non-hazardous. The nature of the product is that when spread over the oil/water mixture can be easily skimmed off after absorption leaving the water clean. There is no smudging of the material, leaving a neat clean-up of the oil. The blended bio-absorbent when compared with other conventional materials, not only out performs in its absorbing capacity, but is non¬toxic and environment friendly and safe. The bio-absorbent once removed after absorption of the oil can be pressed or squeezed to recover the oil which can be recycled and the bio-absorbent can be reused . Packing in the net can be of various types like - brooms, pads, filters, etc to suit different applications. The advantage of the present composition is the ease with which it can be formulated as free disposable pads and lumps or swabs. The bio-absorbent supersedes in its efficiency and performance as presented in the Table -1 of the accompanying drawings. The composition of this invention has a wide application as extractor or restorer of spilled oil leakages, floating on various surfaces ranging from sea water, land buildings to oil rigs as well as a media for effective bio-remediation. The process involves : Selecting suitable cotton fibres for use in the process and product of this invention The cellulosic fibres, basically cotton can be classed by grade or staple length, micronaire reading to indicate the fineness. The cotton fibres that can be transformed and used as bio-absorbent are modified khora cotton, stretch cotton used in medical and apparel fields, wrinkle free cotton, muslin cloth, silk cotton and the like. The final selection depends upon its absorption capacity and bio-transformation ability .It must be capable of preventing the release of petroleum products into an aqueous environment during transport or storage by curtailing spills. Several types of absorbent media that act as a sponge to hold the oil within and not being affected by chemical composition of oil and that can be drained off easily and subsequently disposed safely and cost effective. The hydrocarbons present in the oil are effectively reduced, or transformed to.acceptable norms. Cleansing : This involves the dusting of the selected cotton fibres. Basically it is loose beating of the fibres in a vertical cylinder that houses a shaft with four rotating pegs. The loose trashes gets dusted out and it increases the surface area of the fibres to a limited extent. The Cotton fibres that are selected for bio-absorbent properties are blended in ratio of 1:1 of Type "A" and Type "B". Type "A" has trash of 20% while Type "B" has 12-15%. The staple length is around 12-20 mm. in Type "A" while it is 21-23 mm. in Type "B". The micronaire value is 2.5 to 4.5 in Type "A" and 3.5-5 in case of Type "B" while Gm/Tex ranges from 9-14 in case of Type "A" and 12-20 in Type "B". This blend with the above specification showed maximum loosening and airspace availability for taking in 0il. Increasing the surface area by incorporaping microbes : The bio-absorbent basically being cellulosic in nature is further softened and loosened by injecting mesophilic, aerobic bacteria and fungus that are celluolytic in nature. The organisms are grown in a carbohydrate rich media and the dense inoculum is transferred to the cellulosic material. The organisms are grown at room temperature. Drying : The softened fibres are then allowed to dry in a loose circulatory rotary beating device that works on 15 HP motor. The shaft with a propeller helps in separation of the fibres. The material is dried completely. All along the temperature is maintained around 25°-35°C. Homogenization of the fibres : The fibres get homogenized further in a rotating tumble dryer. Alternative equipments like spray drying or low temperature fluidised bed can also be used but might not be cost effective. Increasing the hydrophobicity with microbes ; Microbes influence the properties of the fluids and help in oil mobilisation. They also can change the physical/chemical nature of oil. There can be a change in the viscosity and reduction in interfacial tension. Some of the microbes that are heavily used in oil slicks and other polluting areas are Yeasts, Pseudomonas, Escherichia, Arthrobacter, Mycobacterium, Desulfotomaculum. The hydrocarbon constituents of the petroleum are used and the oil globules adhere to the microbes. The organisms used are aerobic, mesophilic and hydrophobic in nature. The theory behind the use of the micro-organisms is as follows. Aerobic micro-organism cells nucleus is encapsulated in a microcapsule that is capable of degrading hydrocarbons. The micro organisms may be bacterial in nature that degrade petrochemicals of genus bacillus, Micrococcus, Arthrobactor, Nacardis, Sacchromyces, Aspergillus Niger, Aorzae or other species. The nucleus surrounded by cell walls has nutrients to sustain growth. The nutrients surrounded by cell walls have nutrients to sustain growth. The nutrients present in the aqueous solution penetrate or dissolve the wall of bacterium and facilitates region of the celluloscopic fibres. They have natural affinity for oleophilic substrates. Therefore, when exposed to water/oil media, they are able to quickly absorb oil from water. The organisms are grown on simple carbohydrate sources with peptone and some trace elements. The nutrients vary according to the microbes and a consortia of the microbes is formulated and injected. The condition of growth are manipulated and carefully controlled for maximising the adsorption. The bio-abosrbent is very light having a density of 0.4-0.8 and is dry and highly porous. The microbes are maintained in agar slants at 5°C. They are grown in shaker flasks where 500 ml. of the broth is prepared for bench scale trials. In case of pilot-scale trials involving inoculants of large size, fermenters are deployed. Microbial analysis done intermittently shows the growth of the organisms on the bio-absorbent. The bio-absorbent is filled in a net like material of various shapes and sizes. With the present biosorbent, which is basically cellulosic fibres, is very easy to handle. The brooms or mattresses can be squeezed in any corner and is absolutely ecofriendly. The biosorbent with its hydrophobic microbes instantaneously absorb the oil that can be brought out and oil squeezed thoroughly in a filter press. The microbes are maintained in agar slants at 5°C. They are grown in shaker flasks where 500 ml. of the broth is prepared for bench scale trials. In case of pilot-scale trials involving inoculants of large size, fermentors will be deployed. Microbial analysis done intermetently shows the growth of the organisms on the biosorbent. The media for the growth of the micro-organisms consists of 0.5-.l.% carbohydrate source, which generally is mannitol, saccharine, dextrose, cellulose, glycerol. Besides carbohydrate 0 .05 to 0.1% peptone along with with trace amounts of amino acids like ,alanine, biotin or leucine and trace amounts of magnesium sulphate, ammonium molybdate, ferric chloride/sulphate, or calcium chlroide are used , for peparing 500ml of broth. Trace amounts of antibiotics like streptomycin or penicillin are also used. Expression of organisms: The microbes after 24 hour incubation, when tested on nutrient agar gives a count in the range of 10x10 to 10x12 /ml (note: this is 10 raised to 10 and 10 raised to 12) of the broth. The expression of the microbes after inoculation and incubated for 24 hrs. into the bio-absorbent ranges from 10 raised 4-10 raised 8 /gm of the bio-absorbent. The biosorbent is filled in a net like material of various shapes and sizes. The preferred embodiments are formed in varying weight and densities. The remediating agents i.e. the bio absorbent material in accordance with this invention can be incorporated within the petroleum products before a spill occurs, remediating agents contained in capsules, coated pellets or pods having varying densities. These capsules or pellets are reclaimable when not activated or not reused. Reclamation can be through centrifugation, precipitation, vaporization or heat treatment. The petroleum consuming aerobic microorganisms can also be activated in case of pipeline spills, whether pipeline is above around or buried below. This also applies when petroleum sinks below water surface as may occur in sea spills. The absorbent micro organism pots or filters can be installed in a vessel carrying petroleum or at the well head, in a pipe line, during loading of oil in a cargo hold or at any other appropriate place, before an oil spill develops or discharge occurs. The bio-absorbent quilts can be spread through a body of petroleum products in transport or storage. Microbes can be aspirated at the well heads of a petroleum body or a pipe line. Besides the bio-absorbents can be used in garages where there is always over spill of the tanker while filling petrol. The bio-absorbents can also be used in absorbing kerosene, lubricant oils and other fuel oil where the oil washed out is very high. For example a granite manufacturer has nearly 50% of kerosene being washed out along with spent wash, which can be recovered by the bio-absorbent in accordance with this invention . 70 to 80% of kerosene can be easily recovered from the absorbent. Similarly the bio-absorbent can be used in garages, bullock cartwheels where oil is used for lubrication. The bio- absorbent in accordance with this invention was tested with high medium and low viscous lubricant oil. The bio-absorbent was also tested on vegetable oil, where again the absorption ratio of 1:10 was noted. The bio-absorbent was also capable of taking in spent oil, which when spilt on any water body's river or sea can be sorbed before seeping to the ground. PILOT PLANT TRIALS OF THE BIO-ABSORBENT IN ACCORDANCE WITH THIS INVENTION Three different types of substrates contaminated with different oils were taken to observe the absorbance of oil by the bio-absorbent in accordance with this invention and the results are demonstrated as shown in the attached graphs in figure 1 and 2 of the accompanying drawings. GRANITE CUTTING INDUSTRY In a granite cutting industry, the problem faced by them is the excessive abrasion and exposure to granite dust while granite is being cut or chistled with special blades. In order to control this problem, they use kerosene oil and water is used in large quantities, to wash away the dust. The sludge created by the use of kerosene and oil to trap the dust needs to be disposed off safely as it contaminates soil that supports vegetation. Therefore, the bio-absorbent in accordance with this invention was specially tried to absorb kerosene from the sludge, leaving the dust to settle in the earth. The objective was two fold. By using the bio-absorbent in accordance with this invention as loose flakes, not only the kerosene gets abserbed, but it could also be retrieved from the flakes in significant amount, which brings down the cost and can also be handled with great ease and safety. Secondly, the contamination of the soil by leaching of kerosene from the sludge could be controlled, leaving the granite dust sludge to be disposed off safely. Procedure: The trials were conducted on 500 meter granite cutting where in 2 hours, 5 liters of kerosene oil and 15 liters of water was utilized. Thin pillow like pads of spoil check were placed at the bottom of the granite stone that was mounted for cutting. The sludge, which is a combination of oil, water and granite dust slowly, got collected on the pads. These pads were picked up at 30 minutes interval and gently squeezed. While the water was collected in a tank, kerosene oil that was absorbed by the pads was retrieved from the pads by squeezing. Out of 5 litres of total kerosene that was absorbed by the bio-absorbent in accordance with this invention, 4.8 litres got collected through 400 gms of the bio-absorbent. It was observed that 96% of kerosene was prevented from getting spoiled and reused in granite processing the ratio of absorbent to absorbance is 1:12. Retrival of Crude oil by absorbents from crude oil sludge at BPCL refinery: Refineries like BPCL normally have oil sludges in their crude oil. Disposing the sludge is a major problem in refineries, which has a very pungent smell of ammonia. 100 kgs of this sludge was taken for pilot plant trials to see if the bio-absorbent in accordance with this invention could be deployed to absorb oil from sludge and making it safe for disposal. These trials were conducted at BPCL refinery, Mahul village, Mumbai. The sludge was free flowing viscous and was taken from the corner of large holding tank. A long handle spade was used to draw the sludge out of the holding tank and collected in plastic tubs. About 20 Kg oily material was taken in plastic tubs. 100 gms size pouches was mixed with the free flowing oil of the sludge that got sorbed on to it. When all oil was absorbed, the bio-absorbent in accordance with this invention were taken out and oil absorbancy ratio was determined all the five tubs of 20 kg batches which was quantified individually for rate of absorption by the bio-absorbent in accordance with this invention . The crude oil content in the sludges is 6 kg per 20 kg of the sludge (i.e. 3o%). It was observed that 5.25 Kg of oil was absorbed by the bio-absorbent in accordance with this invention by 350 gms of absorbent pads. The ratio of the bio-absorbent in accordance with this invention to retrieval of oil was in the range of 1:15. This gives an absorbance efficiency of 87.5%. Retrieval of crude oil from MS sludge by the bio-absorbent in accordance with this invention at BPCL, khau creek installation: 100 Kgs of MS sludge containing 10% crude oil was used to establish the absorbance of interlocked petroleum oil from sludge with the help of the bio-absorbent in accordance with this invention . The oil could be retrieved from the bio-absorbent in accordance with this invention by squeezing it and the remaining sludge bio-degraded. Two Kgs of small bio-absorbent in accordance with this invention check pads was mixed with the above 100 kgs MS.sludge with the help of a long handle fork. The heap was agitated for 20 minutes. Then the sp'oil pads were lifted and placed between steel plates and pressed to remove the oil. 7 Kgs of oil was extracted by 2 Kg of the bio-absorbent in accordance with this invention from a 100 Kg MS sludge batch. The pads after removing the oil was again reused in the sludge to retrieve oil. Then the sludge was biologically degraded by using microbes. The oil sludge after retrieval of 70% oil could be degraded into a dry, free flowing material that had properties of manure and could be used as soil enrichner. The time taken for degradation of the sludge was 62 days and the bacterial counts were in the range of 1010. The percentage of oil retrieved has been presented in the graphs of figure 1 and 2 of the accompanying drawings. . _ _._-._ - - We Claim: 1. A method of making a composition for selectively absorbing oil from a mixture containing such oil, consisting of dusting of cleansed cotton fibres by loose beating of two types, Type A having staple length of 12 to 20 mm, a trash of 20 per cent, micronaire value of 2.5 to 4.5 and a Gm/Tex ranging from 9-14 and Type B having staple length of 21 to 23 mm, a trash of 12 to 15 per cent, micronaire value of 3.5 to 5 and a Gm/Tex ranging from 12-20 in the ratio of Type A to Type B of approximately 1: 1; injecting a micro-organisms which is mesophilic, celluloytic and hydrophobic in nature into the mass of said dusted cotton fibres; drying the said mass of cotton fibres at temperatures ranging from 25 to 35 degrees C; homogenising and fluffing the dried fibres to obtain an oil absorbing mass having a density of 0.4-0.8. 2. The method claimed in claim 1, in which the oil absorbing mass of homogenized dried fibres are enclosed in a net of predetermined shape and size. 3. The method of claim 1, in which, dusting is achieved by loose beating of the fibres in a vertical cylinder that houses a shaft with four rotating pegs. 4. The method of claim 1, in which, the micro-organisms selected are grown in a carbohydrate rich media. 5. The method of claim 1, in which, the fibres are dried in a loose circulatory rotary beating device 6. The method of claim 1, in which, the dried fibres are homogenized in a rotating tumble dryer. 7. The method of claim 1, in which, the dried fibres are homogenized in low temperature fluidised bed. 8. The method of claim 1, in which, the microorganisms are at least one mircoorganism selected from the group containing Yeasts,; Pseudomonas, Escherichia, Arthrobacter, Mycobacterium, Desulfotomaculum aerobic bacteria and fungus. Dated this 15th day of April 2004. MOHAN DEWAN OF R.K.DEWAN & COMPANY APPLICANTS' PATENT ATTORNEY

Documents:

468-mum-2004-cancelled pages (19-04-2004).pdf

468-mum-2004-claims(granted)-(19-04-2004).doc

468-mum-2004-claims(granted)-(19-04-2004).pdf

468-mum-2004-correspondence (25-05-2005).pdf

468-mum-2004-correspondence(ipo)-(17-02-2005).pdf

468-mum-2004-drawing(19-04-2004).pdf

468-mum-2004-form 1(19-04-2004).pdf

468-mum-2004-form 19(29-04-2004).pdf

468-mum-2004-form 2(granted)-(19-04-2004).doc

468-mum-2004-form 2(granted)-(19-04-2004).pdf

468-mum-2004-form 26(19-04-2004).pdf

468-mum-2004-form 3(19-04-2004).pdf

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