Patent Application
20190358592
The present invention relates to a development of gamma nanoalumina particles a well-known adsorbent by low cost process and a simple methodology of incorporation of the developed nanoadsorbent in the conventional sediment removal water filter/cartridges. More particularly, the present invention relates to a method of synthesis of low cost nanoparticle of gamma alumina, a well-known adsorbent for fluoride and arsenic removal and their use in making of gravity operated household device useful for the treatment of up to 250 μg/l (ppb) arsenic and 10 mg/l (ppm) fluoride present in contaminated drinking water. Besides arsenic and fluoride removal, the developed device can also be used for the purification of heavy metals like chromium, lead, cadmium etc. contaminated water. Developed filtration technology is also very effective for maximum removal of bacteria, viruses etc.
Drinking water is a major source of fluoride and arsenic contamination that causes severe health problems. World health organization (WHO) has set the guidelines of 1.5 mg/l fluoride and 10 μg/l arsenic as their permissible limit in potable water. Though, fluoride is beneficial in prevention of cavities formation in the teeth and provides strength to skeleton system but drinking of excessive fluoride contaminated water start dental and skeleton fluorosis problem, whereas, arsenic is entirely a toxic element for human being. In India only, more than seventy million people in nineteen states are suffering from fluorosis problem. Besides India, this problem is also common in countries like USA, China, Japan, Argentina, African and Gulf countries. As per report published in 2002, more than 23 nations have problem of excess fluoride in water [A. K. Shusheela, Proc. Ind Nat. A cad B 689, (2002) 289-400], [E. Kumar, A. Bhatnagar, U. Kumar, M. Sillinapaa, J. Haz. Mater 186 (2011) 1042-48]. Contamination of ground water due to arsenic is equally alarming. As per study in 2007, over 150 million people in more than 70 countries are probably affected by arsenic poisoning of drinking water [S. Shankar, U. Shanker, Shikha, Scientific world journal (2014) 304524]. In India, seven states namely—West Bengal, Jharkhand, Bihar, Uttar-Pradesh, Assam, Manipur and Chhattisgarh state have so far been reportedly affected by arsenic contamination in groundwater. Arsenic-contaminated drinking water causes adverse health effects. Arsenic plays crucial role in making disturbance in RNA and DNA synthesis, which consequently lead to cancer, increasing birth of exceptional child, low birth weight, malformed child and dead births [C. K. Jain, I. Ali, Water Res., 1 (2000) 4304-4312; M. D Kiping et al. Envi. & Man 6 (1997) 93-110; J. C. Negi et al, J. Chemosphere 9 (2003):1353-1359; P. L. Smedley et al. Appl. Geochem 3 (2002) 259-284; R. S. Burkel, R. C. Stoll, Remediation 2 (1999) 114-121]. Arsenite [As(III)] is found primarily as H3AsO3, H2AsO3−, HAsO32−, and AsO33 is more toxic than arsenate [As(V)] and is metabolized faster and easily accumulated in nails and hair [M. Bissen, F. H. Frimmel, Acta Hydrochim, 319 (2003) 9-18]. Due to seriousness of these problems, many technologies for the treatment of arsenic and fluoride contaminated drinking water have been developed during last six decades. But none of them could solve this problem so far to the fullest extent especially their application at household or domestic level.
Well known Nalgonda technique [Nawlakhe, W. G., Kulkarni, D. N., Pathak, B. N. and Bulusu, K. R., Defluoridation of Water by Nalgonda Technique, Indian Journal of Environmental Health, 17 (1975) 26-65] is based on lime, alum treatment process where alum (hydrated aluminum salt) acts as flocculate for adsorption of fluoride or arsenic of water. However, this technique was not successful because of the multistage treatment process, maintenance and generation of a large amount of sludge. Bone char is another prominent defluoridation material, produces by the carbonizing bone at 1200-1600° C. The presence of calcium and phosphate in the bone char posses superior uptake quality for fluoride ion. The fluoride uptake is mainly based on ion exchange in which carbonate radical of the char comprising Ca(PO4)6.CaCO3, is replaced by fluoride ion, forming insoluble fluoroapatite. This is one of the effective materials that used in defluoridation of water in many countries on community treatment level. However, it is costly process and cannot be adopted in developing country like India. Among other methods, reverse osmosis [R. Y. Ning, Desalination 143 (2002) 237-241], ion exchange [F. Vagliasindi, M. M. Benjamin, Water Sci Technol 38 (1998) 337-343] are effective processes for the fluoride or arsenic removal but they are costly process.
TERAFIL water filter developed by Dr Kuntia of CSIR-IIMT, Bhubneswar, is basically made from a mixture of red clay (silt clay), river sand and wood saw dust without using any chemicals. This filter is used for removal of sediments and turbidity of water. Though this filter is cost effective and can be used at household level, it can not be used for arsenic or fluoride removal from drinking water. A filter media developed by Kumar, P. K. Kapur, K. K. Das (Indian Patent Application number 1256/MUM/2003) comprising aluminum hydroxide coated rice husk ash is developed for the removal of fluoride ion from the contaminated drinking water. Fluoride removal capacity of the filter media is reported to be 7-8 mg/g which is not very effective adsorbent materials. The other drawback of the developed filter media is that different stages is involved in the preparation of filter. On the other side ceramic defluoridation filter candle developed by M. K. Dhar (Indian patent, 16/MAS/2000, sification number C04338/00, Ceramic candle and filtration system from treated kimberrlite waste for removal of fluoride from water rich in fluoride content) describe treatment of 20 liter/day of excessive fluoride containing water. The life of candle is estimated to be of two-three months. The filtration device include, a container with multiple holes at the bottom is tided with course cloth to cover the holes, over the cloth calcined & chemically surface treated Kimberlite waste was filled (5 kgs). The above slated system take care of 20 liters of water to average family consumption. After alternate month calcined Kimberlite has to be replaced and candles made from treated Kimberlite has to be replaced after ever three months. The drawback of the filtration device that a huge amount of Kimberlite waste is used which require their often replacement. Generation of a huge amount of exhausted Kimberlite waste is another problem of the developed system,
Fluoride removal based on adsorption process comprises of separation of fluoride ions by adsorption on the alumina surface [Fink, G. J. and Lindsay, F. K. (1936), Activated alumina for removing fluorides from Drinking Water, Industrial and Engineering, 28(9), 947-948]. Activated alumina which presents in its gamma phase posses more surface area and thus more effective for the removal of fluoride or arsenic or other inorganic toxic element from the water as compared to other known adsorbents. After saturation with theses contaminants fluoride ions, it can be regenerated using low cost non toxic chemicals like NaOH, H2SO4 and HCl. Fluoride removal from ground water by gamma alumina coated honeycomb at 11 mg/g removal rate is reported [K. Dash, U. S. Hareesh, R. Johnson, J. Arunachalam, Water Practice and Technology, IWA Publishing 2011 doi:10.2166/wpt.2010.061]. A number of patents have been filed for removal of arsenic of water using adsorption based filtration technology. An improved water treatment technology for removal of arsenic, iron and phosphate by zero valent iron and reactor developed by Khillar et al [Indian patent application 2336/Mum/2008] can be operated with and without electricity. The said reactor comprising complex unit containing zero valent iron unit and filtration system. Another patent submitted by Viswnath Pal [Indian patent application number 341/KOL/2003] comprising passing arsenic contaminated drinking water through first an iron filter selected from gravel, sand and manganese dioxide and subsequently through a container having granular ferric hydroxide etc. for obtaining arsenic free water. The said treatment system is complex and can be operated without electric power. Another Indian invention related to development of household water filter comprising ferric hydroxide coated rice husk ash as adsorbent for the removal of arsenic from water [Vivek Ganvir et al. Indian patent application number 1257/MUM/2003]. Though, the developed filter has simplicity for water filtration but coating of iron hydroxide over rice husk ash particles is tedious, multistep process and difficult to make at low cost in commercial level.
Further, reports by USEPA, 2003 suggest that activated alumina is the best material to reduce fluoride level below 1.5 mg/l (ppm), because it has got good affinity and selectivity for fluoride. However, use of large quantity of activated alumina in the column requires a lot of times in regeneration, choking of the column, are the main draw backs for the use of activated alumina for arsenic and fluoride removal of water. Because bigger particle size (0.4-1.2 mm), the adsorbent capacity of activated alumina for fluoride occurs very low (˜2-4 mg/g). However, smaller particle size of alumina can increase the surface area and additionally it will have better mass transfer efficiency. It has been observed that nanoparticles of gamma alumina show better efficiency than activated alumina particles present in micrometer sizes [E. Kumar, A. Bhatnagar, U. Kumar, M. Sillinapaa, J. Haz. Mater 186 (2011) 1042-48]. Since nanoparticles have proven themselves as excellent adsorbents due to their unique features like high catalytic potential and reactivity, large surface area etc, its small quantity could be sufficient for the treatment of fluoride or arsenic contaminated drinking water in a large volume. Recently I. B. Singh and Archana Singh [Indian patent submitted Ref. No. 0056NF2016] have developed low cost nanoalumina particles that could remove fluoride from water at 20-25 mg/g rate. It was observed that nanoadsorbent based household defluoridation device can treat 3000-4000 liter 2-3 mg/l fluoride contaminated water using one kg of synthesized low cost nanoadsorbent Indian patent submitted Application No. 201811019279). Present patent is an improved version of earlier developed nanoadsorbent based defluoridation device that can remove both, fluoride as well as arsenic, is being submitted for its publication.
The main object of the present invention is to incorporate synthesized nanoparticles of gamma alumina into the conventional polypropylene make sediment removal cartridges which should work on gravity based filtration at 1-5 lit/h filtration rate.
Another important object of the invention is to make simple water filtration household device that should contain two or three number of nanoalumina incorporated cartridges and each cartridges should contains 130-150 g nanoparticles.
Yet another object of the present invention is to optimize flow rate of the developed household domestic device in such a way that maximum arsenic or fluoride adsorption occurs at the filtration rate in the range of 1 to 5 lit/h filtration rate.
Still another object of the filtration device that it should work on gravity force and no electricity require for the working of the device.
Yet another object of the filtration device that it should be compact and space saving in design.
Yet another object of the filtration device that one simple sediment removal cartridge should also be attached before entering water into nanoalumina incorporated cartridges to remove water turbidity and avoid choking problem of the device.
Present invention relates to development of a methodology of incorporating nanoparticles of well known gamma alumina adsorbent developed by a cost effective method, in conventional sediment removal water cartridges make of polypropylene sheet (porosity 10-20 micron make cylindrical cartridges/filter: 7 inch length, 1-2.5 inch dia). 130-150 g synthesized low cost (˜10 USD/kg) nanoparticles of gamma (γ) alumina of 20-30 mg/g fluoride adsorption capacity and 25-30 mg/g arsenic adsorption capacity, was incorporated successfully in the sediment removal cartridges/filter. Afterward, a simple household filtration device containing nanoalumina incorporated two or three cartridges arranged in series, overhead tank for keeping arsenic or fluoride contaminated water and treated water storage container was made.
The developed filtration device can filter water at 1-5 lit/h filtration rate without electricity. Present invention demonstrates a simple method of incorporation of nanoadsorbent in the conventional sediment removal filter and making of a household filtration device that can be used for treatment of arsenic or fluoride contaminated ground/drinking water. Two or three number of 130-150 g nanoalumina incorporated cartridges made filtration device can treat 50-100 μg/l arsenic contaminated 4000-10000 liter water and 2-5 mg/l fluoride contaminated 3000-6000 liter drinking water after 2-3 regenerations.
Two or three number of cartridges (size 7 inch in length and 1-2.5 inch in dia) containing 130-150 g incorporated nanoalumina are kept in housing in series whose inlet is attached to the overhead tank containing contaminated water and outlet is connected in plastic container where treated water is stored. The treatment cost is estimated to occur around 0.15-0.25 USD/100 liters for 50-100 μg/l arsenic and 0.25-0.50 USD/100 liters for 2-5 mg/l fluoride contaminated water.
In an embodiment of the present invention, methodology developed for the incorporation of nanoparticles of alumina in sediment removal filter/cartridges, can be adopted for any types of adsorbent. The low cost nanoparticle of gamma alumina is synthesized to bring down fluoride treatment cost significantly low [I. B. Singh, Archana Singh, Indian patent submitted, Application No: 0056NF2016]. Firstly, sodium aluminate was prepared by pure aluminum metal in 2M sodium hydroxide solution. The prepared sodium aluminate is subjected for precipitation reaction under stirring condition and by drop by drop addition of 2M sulphuric acid solution till pH reached at around 7. White gel like precipitates formed which is mainly hydrous aluminum hydroxide Al(OH)3.nH2O. This is heated at a temperature in the range of 480° to 500° C. in muffle furnace for five hours followed by their grinding in mechanized mortar pistil for 5-6 hour to get nanoparticle of gamma alumina of size in the range of 20-25 nm of surface are in the range of around 250-300 m2/g. Finally the adsorption kinetics study of fluoride and arsenic in water was carried out to see the removal potential of the synthesized nanoparticles of gamma alumina. Before incorporating in sediment removal cartridge, fluoride and arsenic adsorption capacity of the synthesized nanoparticles was estimated through adsorption studies, are found as 20-30 mg/g and 25-30 mg/g, respectively.
In another embodiment of the present invention, 130-150 g synthesized nanoparticles of gamma alumina has been incorporated in conventional sediment removal cartridge made of polypropylene cloth sheet. For making cartridge, one end closed perforated polymer make cylindrical tube (dia 30 mm, length 230 mm, thickness 1 mm) is used whose another end was threaded and can be fixed properly in the housing. In making of filter candle, firstly one layer polypropylene make thread is wrapped over the perorated tube (
In this way 140-150 g synthesized nanoparticles of gamma alumina were incorporated in each filter cartridges/candle.
In yet another embodiment of the present invention, household filtration device was made (
In still another embodiment of the present invention, residual fluoride was analyzed by spectrophotometer (Hack39000, method no) using alizarin red visual method and Spand solution whereas arsenic was analyzed using Hack arsenic kit. Alizarin red indicator was prepared using zirconyl chloride octahydrate (ZrOCl2) and mg alizarin red dye (3-alizarin sulphonic acid sodium salt). In the presence of fluoride ions, zirconium ions get replaced by fluoride ion from the complexes resulting in re-appearance of original yellow color of zirconium. Concentration of residual fluoride was determined by comparing color of standard solution of fluoride in water. The intensity of yellow color depends on the concentration of residual fluoride present in the working solution. In preparation of standard solution, blank (0.0), 0.2, 0.4, 0.6, 0.8, 1.0 and 1.2 mg/L fluoride bearing water solutions were prepared in 50 ml volume containing nessler tube. 5 mL of prepared alizarin red indicator was added in each solution which showed different shades of color from dark red (blank) to faded yellow (fluoride bearing). Solutions were also prepared from the filtrates obtained after batch adsorption in identical condition.
In another embodiment of the present invention, the experimental design was customer specified and was modified to understand the performance of candle filter for testing bacteria removal efficiency of the developed cartridges. The removal studies in treated water are done as per U.S. Environmental Protection Agency (USEPA) and NSF International standard using test bacteria—Klebsiella terrigen (1-3×103 CFU/100 ml); Virus—MS2 Bacteriophage (1-3×103 CFU/L); Cyst of Giardia (1-3×103 CFU/L) in 20 liter water which passed through the filter at 1-2 lit/h filtration rate. Bacteria removal studies are done by membrane filtration and standard plate count using selective media method. Virus removal studies are carried out using agar overlay method while cyst removal studies are done by microscopy technique.
130-140 g nanoparticles incorporated both filters candle shown more than 95% fluoride removal (treated water contains 0.5-0.8 ppm) of 5 ppp fluoride containing initial 200 liter of water with filtration rate nearly in the range of 0.8 lit-1 lit/h (20-4 lit in 24 h). Even single filter candle shown more than 90% fluoride removal (treated water contains ˜1 ppm fluoride) of 5-5 pp fluoride containing water with filtration rate of 1 lit/h (24 liter in 24 h). Both filters have also shown fluoride removal capability for 10 mg/l fluoride containing water as more than 90% fluoride removal (treated water contains 0.8-1.0 ppm) was obtained for 10 mg/l fluoride containing water.
As given in example 1, both filters shown more than 90% fluoride removal (treated water contain 0.8-1.0 ppml fluoride) of 5.5 ppm fluoride containing another 200 liter of water (total 400 liter) with filtration rate of 0.8 lit/h (20 lit in 24 h). Single filter candle shown nearly 70 fluoride removal (treated water contain around 1.2-1.4 mg/l fluoride) of 5 ppm fluoride containing water after 400 liter of treatment. Both filter have shown fluoride removal capability of 10 mg/l fluoride containing water as more than 80% fluoride removal (treated water contains 1.3-1.5 ppm fluoride) is obtained after treatment of 400 liter 10 mg/l fluoride water. This indicate that both filter can also treat maximum 350-400 liter water containing more than 10 mg/l fluoride.
As given in example 1, both filters have shown more than 80% fluoride removal (treated water contain 1.1-1.4 ppml fluoride) of 5.5 mg/l fluoride containing another 200 liter of water (total 600 liter). Fluoride removal capability of single filter candle decreases substantially after 500 liter of 5 ppml fluoride containing water as 2.5-3.0 mg/l residual fluoride was obtained in treated water using single filter after treatment of 500 lit Of 5.5 ppm fluoride water. The fluoride removal capability of both filter reduces significantly for treatment of 10 mg/l fluoride water as around 3.0-3.5 ppm residual fluoride was found in treated water of 10 mg/l fluoride containing water.
As given in example 1, both filter shown more than 70% fluoride removal (treated water contain around 1.3-1.5 ppml fluoride) of 5.5 ppml fluoride containing another 200 liter of water (total 800 liter). Occurrence of 1.3-1.5 mg/l in treated water is almost within the WHO prescribed limit of 1.5 mg/l fluoride in drinking water.
As given in example 1, both filter shown more than 60% fluoride removal (treated water contain around 1.6-1.90 ppm fluoride of 5.5 ppml fluoride containing another 200 liter of water (total 1000 liter). Presence of more than 1.5 ppm fluoride in treated water exceeded the WHO guidelines of maximum permissible level of fluoride (1.5 mg/l) in drinking water. Therefore both filters can treat maximum 700-800 lit of 5.5 ppm fluoride water.
As given in example 1-5, concentration the different cations and anions present in the tape water, is found almost same after fluoride removal. This indicates that present synthesized nanolaumina particles shows their ability of fluoride adsorption without affecting concentration of other mineral constituents of water.
As given in example 1-5, a slight turbidity of treated water is observed for initial 2-3 lit of filtration. Afterward filtered water was observed crystal clear without any turbidity. This indicates that incorporated nanoparticles do not diffuse from the nanoparticles incorporated polypropylene cloth in the treated water.
140-150 g nanoparticles incorporated three cartridges containing filtration device shown more than 90% fluoride removal, (treated water contains 0.2-0.7 mg/l fluoride) of 5 mg/l fluoride containing 500 liter of tap water (pH 6.5-8.3, TDS 310-350 mg/l) with filtration rate of 3-5 lit/h. Above device has also shown fluoride removal capability for 10 mg/l fluoride containing water as more than 85% fluoride removal (treated water contains 0.5-1.5 mg/l) was obtained for 10 mg/l fluoride containing water up to 500 liter volume.
140-150 g nanoparticles incorporated three cartridges containing filtration device shown more than 90% arsenic removal (0-6 μg/l) of 100 μg/l arsenic containing initial 1000 liter tap water (pH 8.1-8.3, TDS 310-350 mg/l) with filtration rate of 3-5 l/h. Above device have also shown arsenic removal capability for 250 μg/l arsenic containing water as 500 liter of 250 ppb arsenic containing water can be treated that contains 5-20 μg/l arsenic as residual arsenic in treated water.
As given in example 1, above filtration device has shown more than 85% fluoride removal (treated water contain 0.7-1.0 mg/l fluoride) of 5 mg/l fluoride containing another 500 liter of water (total 1000 liter). The fluoride removal capability of the filtration devices reduces slightly for treatment of 10 mg/l fluoride water as around 1.2-1.6 mg/l fluoride occurred in treated water after treatment of next 500 liter of 10 mg/l fluoride containing water.
As given in example 2, above filtration device has shown more than 90% arsenic removal (treated water contain 6-9 μg/l arsenic) of 100 μg/l ppb arsenic containing another 1000 liter tap water (total 2000 liter).
As given in example 1, developed filter device shown more than 80% fluoride removal (treated water contain around 1.0-1.4 mg/l fluoride) of 5 mg/l fluoride containing another 500 liter of water (total 1500 liter). Occurrence of 1.1-1.4 mg/l in treated water is within the WHO prescribed limit of 1.5 mg/l fluoride in drinking water.
As given in example 2, developed filter device has shown more than 85% arsenic removal (treated water contain around 9-15 μg/l arsenic) of 100 μg/l arsenic containing another 1000 liter of water (total 3000 liter). This concentration of arsenic in treated water is almost nearby in the range of WHO prescribed limit of 10 μg/l arsenic in drinking water.
As given in example 1, developed filter device shown more than 70% fluoride removal (treated water contain around 1.4-1.8 mg/l fluoride) of 5 mg/l fluoride containing another 500 liter of water (total 2000 liter). Presence of this range of fluoride in the treated water is almost equal to the permissible limit of fluoride in drinking water as per WHO guidelines. Therefore developed filter device can treat maximum 1500-2000 lit of 5 mg/l fluoride water before saturation.
As given in example 2, developed filter device remove more than 80% arsenic removal (treated water contain around 10-20 μg/l arsenic) of 100 μg/l arsenic containing another 1000 liter of water (total 4000 liter). Presence of 10 μg/l arsenic fluoride in treated water is around the permissible limit of arsenic in drinking water as per WHO guidelines. Therefore developed filter can treat maximum 3000-3500 lit of 100 μg/l arsenic containing water.
Based on example 7, it is estimated that developed filter device can treat more than 3000-4000 liter of 2-3.0 mg/l fluoride containing water before saturation.
Based on example 8, it is estimated that developed filter device can treat 6000-7000 liter of 50-60 μg/l arsenic containing water before saturation.
As given in example 1-10, concentration of the different cations and anions present in the tap water, is found almost same after arsenic or fluoride removal. This indicates that present synthesized nanolaumina particles shows their strong affinity for arsenic or fluoride of water without affecting concentration of other mineral constituent of water.
As given in example 1-10, a slight turbidity of treated water is observed for initial 5-10 lit of filtration. Afterward filtered water becomes clear without any turbidity. This indicates that incorporated nanoparticles do not diffuse from the polypropylene cloth in the treated water.
As given in example 9, the saturated nanoadsorbent of the filter can be regenerated by use of 1.5-2.0% sodium hydroxide solution and 1.5-2% sulphuric acid or 4-5% aluminum sulphate solution.
As given in example 7 and 13, the regenerated nanoadsorbent of the developed device can further treat another 1000-1500 liter 5 mg/l containing tap water of TDS <300 mg/l and pH 6.5-8.3 range.
As given in example 8 and 13, the regenerated nanoadsorbent of the developed device can further treat another 1200-1800 liter of 100 μg/l arsenic containing tap water of TDS <300 mg/l and pH 6.5-8.5 range.
As given in example 7 and 8, the saturated nanoadsorbent can be regenerated and reused for the fluoride and arsenic removal after three regenerations.
As given in example 1 and 2, nearly 90% removal of bacteria and more than 99% removal of viruses and cyst are observed.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201811019279 | May 2018 | IN | national |
