FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2006
PROVISIONAL SPECIFICATION
(See Section 10 and Rule 13)


A PROCESS FOR MAKING METAL IMPREGNATED CARBON BLOCK FILTERS
HINDUSTAN UNILEVER LIMITED, a company incorporated under
the Indian Companies Act, 1913 and having its registered office
at 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India
The following specification describes the invention


TECHNICAL FIELD
The present invention relates to a process for making metal impregnated bound Carbon block filters.
The invention has been developed primarily for use in gravity-fed water filtration devices for purification of drinking water, and will be described hereinafter with reference to this application. However, it will be appreciated that the invention is not limited to this particular field of use.
BACKGROUND AND RELATED ART
Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of the common general knowledge in the field.
Drinking water contains different contaminants such as particulate matter, harmful chemicals, bacteria, cysts and viruses. It is recommended by health professionals that such contaminants should be removed so that water becomes fit for consumption.
Activated Carbon is useful for the purification of drinking water as it aids in the removal of chemical contaminants, cysts, particulate matter and bacteria. However, activated Carbon particles have rough and porous texture which is capable of providing a favorable and protected surface for bacterial growth. As a result, algae and bacteria colonize the Carbon surface, thus diminishing the surface available to contact the water as well as allowing these organisms to

grow. Even if the water is chlorinated, some bacteria are chlorine resistant. Thus, the activated Carbon actually can promote the growth of bacteria that would not grow in the chlorinated water per-se. The most predominant bacteria that were isolated from such water belonged to the genus Pseudomonas. In addition, bacteria of the genus Bacillus were also found in large quantities.
A method of making bound Carbon block filters for use in water purification has been described in US4753728 (Amway, 1988) in which Carbon particles are bonded into a filter block by a polymeric material having melt index of less than 1 gram per 10 minutes as determined by ASTM (American Society for Testing and Materials) D1238 standard, at 190 °C, and 15 kg load.
CA2396510 (TYK Corp, 2003) describes a process for preparing Carbon filters using particles of size 35-200 u with 50 % or more ceramic binder, in which water is sprayed onto this mixture before it is sintered.
To prevent and/or reduce the occurrence of bacterial colonization on the surface of the Carbon block, such blocks are generally impregnated with a metal such as Silver, Copper or Zinc.
US2847332 (Union Carbide Corporation, 1958) describes a process for impregnating metallic Silver onto a bound Carbon block in which a bound block is dipped into an aqueous solution of Silver nitrate and the Silver ions are precipitated as an insoluble Silver compound by exposing the dipped block to Ammonia fumes to precipitate Silver oxide. This is followed by reduction of the Silver oxide to

metallic Silver by heat treatment. It is said that the process results in impregnated blocks with a uniform distribution of Silver content. This process is suitable for impregnation of higher levels of metals, but the present inventors have found that that blocks made in accordance with this process show variation in the amount of the impregnated metal across different blocks. This variation could become critical when the level of impregnation sought is lower.
On the other hand, in the prior art process, there are two separate steps for block making; a metal impregnation step; and a block making step. The first process is generally done by the suppliers of activated Carbon particles. The two processes are independent of each other and therefore the cost of Carbon block manufacturers increases because the metal impregnated Carbon comes at a cost to the person making the blocks.
The present inventors have found that the above procedure is cumbersome as it is a two-step process. Further, this procedure is not suitable for impregnating lower levels of Silver or other metals, of the order of 0.01 to 5.0 wt%, while still showing relatively low level of variation in metal content across different blocks.
OBJECT OF THE INVENTION
It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art.

It is an object of the present invention to provide a process for preparing a moulded Carbon block filter impregnated with a metal selected from Silver, Copper or Zinc, with relatively low level of variation in metal content across the blocks, relatively lower deviation from the theoretical metal content, and where the leach-rate of metal from the block during use is relatively low.
Other objects of the present invention will become apparent to those skilled in the art by reference to the specification.
The present inventors have surprisingly found that bound Carbon block filters with relatively low level of variation in metal content across the blocks, relatively lower deviation from the theoretical metal content, and relatively lower leach-rate of metal from the blocks during use could be obtained by a process in which the activated Carbon particles are contacted with an aqueous solution of a salt of the metal in the presence of Ammonium hydroxide, followed by the addition of a polymeric binder and finally moulding the block by application of pressure and heat.
Uniform metal impregnation happens during the process of molding by heat and pressure. The inventors have also observed that this process offers high cost savings due to reduction in energy consumption. It was also observed that surprisingly the impregnated blocks made by the process according to the invention, showed relatively higher absorption of organic contaminants when compared with the conventional metal impregnated Carbon blocks.

SUMMARY OF THE INVENTION
According to the first aspect of the invention there is provided a process for making metal a impregnated Carbon block filter comprising the steps of:
(i) contacting activated Carbon particles with an aqueous solution of a salt of Silver, Zinc or Copper in the presence of Ammonium hydroxide, to form an aqueous mix; (ii) mixing said aqueous mix with a binder having Melt Flow Rate less than 5 g/10 minutes to form a mixture; (iii) adding said mixture to a mould; (iv) heating said mould to a temperature in the range
of 150 to 350 °C; and, (v) de-moulding the Carbon block filter.
It is preferred that the activated Carbon particles are contacted with an aqueous solution of Silver nitrate, Zinc nitrate or Copper nitrate.
It is particularly preferred that the activated Carbon particles are contacted with an aqueous solution of Silver nitrate.
Preferably the concentration of Silver nitrate in the aqueous solution is in the range of 0.01 to 10 %.
It is also preferred that the mixture in the mould is compressed before heating the mould.


According to the second aspect of the invention there is provided a metal impregnated Carbon block filter obtainable by the process according to the first aspect.
The term "comprising" is meant not to be limiting to any subsequently stated elements but rather to encompass non-specified elements of major or minor functional importance. In other words the listed steps, elements or options need not be exhaustive. Whenever the words "including" or "having" are used, these terms are meant to be equivalent to "comprising" as defined above.
Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material ought to be understood as modified by the word "about".
It should be noted that in specifying any range of concentration or amount, any particular upper concentration can be associated with any particular lower concentration or amount.
For a more complete understanding of the above and other features and advantages of the invention, reference should be made to the following detailed description of preferred embodiments.
DETAILED DESCRIPTION
The expression wt% used throughout the specification means percentage by weight.

Activated Carbon particles are preferably selected from one or more of bituminous coal, coconut shell, and wood and petroleum tar. It is preferred that surface area of the activated Carbon particles exceeds 500 m2/g, more preferably exceeds 1000 m2/g. It is preferred that size uniformity co¬efficient of the activated Carbon particles is less than 2, more preferably less than 1.5. It is preferred that Carbon Tetrachloride (CC14) number of the activated Carbon particles exceeds 50 %, more preferably exceeds 60 %. Preferably Iodine number of the activated Carbon particles is greater than 800, more preferably greater than 1000. It is preferred that not more than 5 % of the activated Carbon particles pass through a sieve of 150 mesh, and not more than 5% particles are retained on a sieve of 12 mesh. It is further preferred that not more than 5 % by weight of the activated Carbon particles pass through a sieve of 75 mesh and not more than 5% by weight is retained on a sieve of 30 mesh. It is particularly preferred that less than 1% activated Carbon particles pass through a sieve of 200 mesh.
The Melt Flow Rate (MFR) of the binder is less than 5 g/10 minutes, preferably less than 2 g/10 minutes, and more preferably less then 1 g/10 minutes. Bulk density of the binder is preferably less than or equal to 0.6 g/cm3, more preferably less than or equal to 0.5 g/cm3, and most preferably less than or equal to 0.25 g/cm3. Preferred binder is selected' from Ultra High Molecular Weight Polyethylene or Ultra High Molecular Weight Polypropylene, which have these low MFR values. Their molecular weight is preferably in the range of 106 Daltons to 109 Daltons. Binders of this class are commercially available under the trade names HOSTALEN™ from Tycona GMBH, GUR, SUNFINE™ (from Asahi, Japan), HIZEX™ (from Mitsubishi) and from Brasken

Corp (Brazil) . Other suitable binders include LDPE sold as LUPOLEN™ (from Basel Polyolefins) and LLDPE from Qunos (Australia) .
The melt-flow rate of the binder is measured using ASTM D 1238 (ISO (International Organization for Standardization) 1133) test. This test measures the flow of a molten polymer through an extrusion plastometer under specific temperature and load conditions. The extrusion plastometer consists of a vertical cylinder with a small die of 2 mm at the bottom and a removable piston at the top.
A charge of material is placed in the cylinder and preheated for several minutes. The piston is placed on top of the molten polymer and its weight forces the polymer through the die and on to a collecting plate. The temperature for testing the present polymeric binder material could be chosen at 190 °C and the load at 15 kg. The amount of polymer collected after a specific time interval is weighed and normalized to the number of grams that would have been extruded in 10 minutes; melt flow rate is thus expressed in grams per 10 minutes.
It is preferred that the ratio of the activated Carbon particles to the binder is from 2:1 to 10:1 parts by weight, more preferably from 2:1 and 8:1 parts by weight.
The activated Carbon particles are contacted with an aqueous solution of a salt of Silver, Zinc or Copper in the presence of Ammonium hydroxide, to form an aqueous mix. It is preferred that the activated Carbon particles are contacted with an aqueous solution of Silver nitrate, although it is also possible to use other Silver salts such as Silver

chloride or Silver iodide. Preferably the concentration of Silver nitrate in the aqueous solution is in the range of 0.01 to 10 wt%, more preferably 0.02 to 5 wt% and most preferably 0.02 to 3 wt%. In the case of Silver impregnation, the level of impregnation of Silver in the activated Carbon particles is preferably in the range of 0.01 to 5 wt%, more preferably in the range of 0.02 to 2 wt%, and most preferably in the range of 0.05 to 1 wt%. It is particularly preferred that the level of Silver impregnation is 1 wt%. It is also possible to impregnate Zinc, Copper, a mixture of Silver and Copper, mixture of Silver and Zinc, mixture of Copper and Zinc, or a mixture of Silver, Copper and Zinc by appropriate selection of the salts. The preferred ratio of Ammonium hydroxide to the salt of Silver is in the range of 1:2 to 1:10, more preferably in the range of 1:3 to 1:5, and most preferably in the range of 1:2 to 1:3.
In the case of Copper and Zinc, the level of impregnation is preferably in the range of 0.01 to 10 wt%, more preferably in the range of 0.01 to 5 wt% and most preferably in the range of 0.01 to 2 wt%. The preferred ratio of Ammonium hydroxide to the salt of Copper is in the range of 1:0.05 to 1:2, more preferably in the range of 1:0.1 to 1:1, and most preferably in the range of 1:0.1 to 1:0.7. In the case of salt of Zinc, the preferred ratio of Ammonium hydroxide to the salt is in the range of 1:0.2 to 1:5, more preferably in the range of 1:0.4 to 1:3, and most preferably in the range of 1:0.5 to 1:1.5. Apart from the nitrate salt, it is also possible to use other Copper/Zinc salts, such as chloride or iodide.

It is preferred that the concentration of Ammonium hydroxide in water is in the range of 0.1 to 10 wt% and preferably in the range of 0.1 to 5 wt%.
It is preferred that the ratio of the activated Carbon particles to the agueous solution of the salt of Silver, Zinc or Copper is in the range of 1:0.4 to 1.1.2 and more preferably in the range of 1:0.4 to 1:1.
The activated Carbon particles are mixed with an aqueous solution of the salt of Silver, Zinc or Copper in the presence of Ammonium hydroxide, to obtain an aqueous mix. The mixing is preferably done in vessels which include an agitator, mixer with dulled impeller blades, ribbon blender, rotary mixer or any other low shear mixer that does not significantly alter the particle size distribution. The mixing is carried out to prepare a uniform mix of the Carbon particles. The binder is then added to the above aqueous mix and is further mixed to obtain a mixture. Mixing is preferably carried out for at least 5 minutes, more preferably from 5 to 10 minutes. This mixture is optionally vibrated for a short period, e.g. for 3 to 10 minutes to compact the mixture before moulding. The vibratory compaction is preferably carried out in a vibrator having frequency in the range of 30 to 100 Hz. This process step is preferably carried out for a period of at least one minute, more preferably for 3 to 10 minutes. The mass, whether or not compacted by vibration, is then placed in a mould of pre-selected size and shape and is compressed with pressure not more than 20 kg/cm2, preferably from 3 to 15 kg/cm2 and most preferably from 4 to 10 kg/cm2. The pressure is preferably applied using either a hydraulic press or a pneumatic press, more preferably a hydraulic press. The

mould is preferably made of Aluminium, cast iron, steel or any material capable of withstanding temperatures exceeding 400 °C. The mould is heated to 150 to 350 °C, preferably in the range of 200 to 300 °C. The mould is kept heated for more than 60 minutes, preferably from 90 to 300 minutes. The mould is preferably heated in a non-convection, forced air or forced inert-gas convection oven. The mould is then cooled and the moulded filter is released from the mould. Preferably, a mould release agent is coated on the inside surface of the mould. The mould release agent is preferably selected from Silicone oil, Aluminium foil, or the mould can be coated with suitable materials like Teflon or any other commercially available mould release agent that has little or no adsorption onto the filter medium.
Further details of the invention, its objects and advantages are explained hereunder in greater details with reference to the following non-limiting examples. It would be apparent to a person skilled in the art that many such examples are possible and the examples given under are for illustrative purpose only. These should not be construed so as to limit the scope of this invention in any manner.
EXAMPLES
EXAMPLE-1μ
Process for making Silver impregnated Carbon block filters
A Silver impregnated activated Carbon block filter according
to the invention was prepared by using 30 kg activated
Carbon particles (particle size in the range of 500 u to
1400 μ) supplied by Active Carbon (India) . The activated

Carbon particles were contacted with 20 litres of an aqueous solution of 0.3 wt% Silver nitrate. Ammonium hydroxide was then added to this solution so that its concentration in the solution was 0.1 wt%. The ratio of the concentration of Ammonium hydroxide to that of Silver nitrate was 1:3. This aqueous solution was transferred to a ribbon blender at ambient temperature and mixed under 4 0 RPM (revolutions per minute) and the activated Carbon particles were added. The activated Carbon particles and the above aqueous solution were mixed for about 5 minutes to obtain an aqueous mix. To this aqueous mix, 4.9 kg of Ultra High Molecular Weight Polyethylene with MFR - 0 g/10 minutes, and having bulk density of 0.45 g/cm3 from Asahi Corporation (Japan) were added under mixing, to form a mixture. The above ingredients were mixed for another 5 minutes. The mixture was then removed and about 600 g of this mixture was added to a mould. The mixture was compacted in the mould using hydraulic press to a pressure of 5 kg/cm2 and cured in a hot air oven at 250 °C for about 150 minutes. The hot moulds containing the Carbon blocks were cooled for atleast 30 minutes and then de-moulded. The theoretical Silver content was 0.1 wt%.
In a similar manner, a comparative Carbon block filter made from commercially available Silver impregnated activated Carbon particles (i.e. pre-impregnated activated Carbon particles) with identical properties as in Example-1, (purchased from Active Carbon (India)) having 0.1 wt% Silver was made. In this comparative filter block, the procured activated Carbon particles were already impregnated with Silver metal and then the particles were made into a block using Ultra High Molecular Weight Polyethylene binder, pressure and heat, as done above. The amount of the binder
μand the process parameters were kept the same as above. Commercial Silver impregnated activated Carbon particles which are available from suppliers of activated Carbon particles are generally made by impregnating the particles in an aqueous solution of soluble Silver salts, and subsequently drying in an oven at 110-120 °C for very long period of time typically, 15 to 16 hours).
EXAMPLE-2
Analysis of Silver content of the Carbon block filter made in Example-1 v/s comparative Silver impregnated Carbon block
filters
The Silver content of the Carbon block filter made in Example-1 was estimated by a well known procedure which involved extraction with Perchloric acid followed by Atomic Adsorption Spectroscopy (AAS) measurement, according to EPA (Environmental Protection Agency of USA) ref no 200.9. The theoretical Silver content in the Carbon block of Example-1 was 0.1 wt%. This was compared against the average Silver content of the comparative Silver impregnated Carbon block filters made in Example-1. The values of the average Silver content of three Carbon block filters for each case, (which was the average of three replicate analyses for each block) is given in Table-1 below.
Table-1

Commercial Carbon block filter % average
Silver
content Example-1 Carbon block filter % average
Silver
content
Block 1 0.076 Block 1 0.10
Block 2 0.071 Block 2 0.10
Block 3 0.081 Block 3 0.095


The data in the table above indicates relatively low variation in average Silver content in the case of Carbon block filter of Example-1 made according to the invention. The comparative Carbon blocks, on the other hand, showed inconsistent Silver content and a higher deviation from the theoretical value, which was 0.1 wt%. From the values, the variation in average Silver content of the block filter of Example-1 and the comparative block filters {and it's deviation from the theoretical Silver content of 0.1 wt%) can be appreciated.
EXAMPLE-3
Adsorption of Organic contaminants present in water by the Carbon block filters according to the invention
For this experiment, a Carbon block filter of Example-1 (which was made according to the invention) was fitted inside a gravity-fed water purification device containing a top and a bottom chamber. The filter was fitted inside the top chamber. The bottom chamber had a provision for outlet of treated water. In this experiment, 1500 litres of water containing 5.4 ppm (parts per million) of a heterocyclic organic contaminant (Triazine) was periodically added to the top chamber of the device. In this way, it was made to pass through the Carbon block filter and the treated water which collected in the bottom chamber was periodically analysed for the content of the heterocyclic organic contaminant (Triazine) by the standard HPLC (High Performance Liquid Chromatography) method to check for any reduction in its level after passing through the filter. In a comparative example, 1500 litres containing the same level of the above contaminant were passed through another device in which the

comparative Carbon block filter {having theoretical value of 0.1% Silver impregnation) was fitted. The amount of the contaminant in the water was determined at regular intervals by collecting the treated water from the outlet. The results are shown in Table-2 below.
Table-2

Comparative block filter/ litres of water passed Concentration of the organic contaminant/
ppm Carbon block filter (of Example-1) according to the invention/ litres of water passed Concentration of the organic contaminant/ ppm
700 0.93 700 0.50
1200 1.99 1200 0.93
1500 2.49 1500 0.98
% Adsorption by the block filter at the end of 1500 litres 70.64% % Adsorption by the block filter at the end of 1500 litres 86.5%
The data in the above table indicates that the adsorption of the Carbon block filter according to the invention was about 16% higher than comparative block filter.
EXAMPLE-4
Experiment on leaching of Silver from the impregnated Carbon block filter according to the invention
In the case of metal impregnated Carbon block filters, it is essential that its impregnated metal stays firmly inside the block and the leach rate into the water being filtered is minimal. For this reason, the extent of leach of the metal is often determined and reported in parts per billion (ppb). In another set of experiments, the leach-rate of Silver from

the Carbon block filter (according to the invention) was compared against the comparative block filter. The amount of Silver was determined at regular intervals while 1200 litres of water was passed separately through both the Carbon block filters, which were fitted in separate gravity-fed water purification devices as in Example-3. The Silver content was determined by a method well-known to a person skilled in the art. The results are shown in Table-3 below.
Table-3

Comparative block filter/ litres of water passed Silver content in the output water/ppb Carbon block filter